CN115877657A - Composition for forming organic film, method for forming pattern, compound for forming organic film, and polymer - Google Patents

Composition for forming organic film, method for forming pattern, compound for forming organic film, and polymer Download PDF

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Publication number
CN115877657A
CN115877657A CN202211182821.2A CN202211182821A CN115877657A CN 115877657 A CN115877657 A CN 115877657A CN 202211182821 A CN202211182821 A CN 202211182821A CN 115877657 A CN115877657 A CN 115877657A
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film
forming
organic film
organic
pattern
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郡大佑
山本靖之
小林直贵
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
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    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
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    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
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    • G03F7/26—Processing photosensitive materials; Apparatus therefor
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    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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Abstract

The invention provides a composition for forming an organic film, a pattern forming method, a compound for forming an organic film and a polymer. The solution of the present invention is a composition for forming an organic film, which is characterized by containing an organic film-forming material represented by the following general formula and an organic solvent.
Figure DDA0003865932460000011
In the general formula, R 1 Is a hydrogen atom, an allyl group, or a propargyl group, R 2 Represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a straight, branched or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group or a trifluoromethyloxy group; m =0, 1,n =1, 2,l =0, 1,k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms; each V independently represents a hydrogen atom or a linking moiety.

Description

Composition for forming organic film, method for forming pattern, compound for forming organic film, and polymer
Technical Field
The present invention relates to a composition for forming an organic film, which can be used for fine patterning by a multilayer resist method in a semiconductor device manufacturing process, a pattern forming method using the composition, and a compound and a polymer used for the composition for forming an organic film.
Prior Art
With the high integration and high speed of LSI, the miniaturization of pattern size is rapidly progressing. With the miniaturization of the lithography technology, the formation of a fine pattern has been achieved by shortening the wavelength of a light source and appropriately selecting a resist composition corresponding thereto. The positive photoresist composition used in a single layer is used as a core. The single-layer positive photoresist composition is characterized in that a resist resin is provided with a skeleton having etching resistance to dry etching by chlorine-based or fluorine-based gas plasma, and a switching mechanism (switching) for dissolving an exposed portion is provided, whereby the exposed portion is dissolved to form a pattern, and a substrate to be processed is dry-etched using the remaining resist pattern as an etching mask.
However, when the film thickness of the photoresist film to be used is kept fine, that is, when the pattern width is further reduced, the resolution performance of the photoresist film is lowered, and when the photoresist film is subjected to pattern development by a developer, the so-called aspect ratio becomes too large, which results in a problem of pattern collapse. Therefore, the photoresist film is also gradually thinned with the miniaturization of the pattern.
On the other hand, in the processing of a substrate to be processed, a method of processing the substrate by dry etching using a photoresist film having a pattern formed thereon as an etching mask is generally used, but there is actually no dry etching method capable of obtaining a complete etching selectivity between the photoresist film and the substrate to be processed. Therefore, there is a problem that the resist film is damaged and broken during the processing of the substrate to be processed, and the resist pattern cannot be accurately transferred to the substrate to be processed. Therefore, as the pattern is miniaturized, the photoresist composition is also required to have higher dry etching resistance. On the other hand, in order to improve resolution, a resin used for a photoresist composition is required to have a small light absorption at an exposure wavelength. Therefore, the resin is changed to a novolak resin, polyhydroxystyrene, or a resin having an aliphatic polycyclic skeleton in response to the shortening of the exposure light into i-rays, krF, or ArF, and the etching rate is actually high under the dry etching conditions for substrate processing, and recent photoresist compositions having high resolution tend to be rather weak in etching resistance.
Because of this fact, it becomes necessary to subject the substrate to be processed to dry etching processing through a thinner photoresist film having weaker etching resistance, and it is important to ensure the material and processing in this processing step.
As one method for solving such a problem, there is a multilayer resist method. This method includes a method of interposing an intermediate film having a different etching selectivity from a photoresist film (i.e., an upper resist film) between the upper resist film and a substrate to be processed, obtaining a pattern in the upper resist film, transferring the pattern to the intermediate film by dry etching using the upper resist film pattern as a dry etching mask, and transferring the pattern to the substrate to be processed by dry etching using the intermediate film as a dry etching mask.
As one of the multilayer resist methods, there is a 3-layer resist method which can be performed using a general resist composition used in the single-layer resist method. In the 3-layer resist method, for example, an organic film such as novolak is formed as a resist underlayer film on a substrate to be processed, a silicon-containing film is formed thereon as a silicon-containing resist intermediate film, and a general organic photoresist film is formed thereon as a resist overlayer film. In the dry etching by fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity with respect to the silicon-containing resist intermediate film, so that the resist upper layer film pattern can be transferred to the silicon-containing resist intermediate film by the dry etching by fluorine-based gas plasma. According to this method, even if a resist composition in which it is difficult to form a pattern having a sufficient film thickness for directly processing a substrate to be processed or a resist composition having insufficient dry etching resistance for processing a substrate is used, if a pattern can be transferred to a silicon-containing film (resist intermediate film) and then the pattern can be transferred by dry etching using an oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer film) such as a novolak having sufficient dry etching resistance for processing a substrate can be obtained. Many resist underlayer films are known as described above, for example, as described in patent document 1.
On the other hand, in recent years, studies have been actively made on the manufacture of semiconductor devices having a new structure such as a multi-gate structure, and in response to this, a resist underlayer film is required to have more excellent planarization characteristics and filling characteristics than ever before. For example, when a substrate to be processed as a base has a micro pattern structure such as a hole, a trench, and a fin, it is necessary to use a characteristic that a resist underlayer film is buried in a film (gap-filling) pattern without a gap. When the substrate to be processed as the base has a step, and when a pattern dense portion and a region without a pattern are present on the same wafer, the film surface needs to be planarized by a resist underlayer film (planarization). By flattening the surface of the lower layer film, it is possible to suppress variation in film thickness of the resist intermediate film and the resist upper layer film formed thereon, and to suppress a decrease in the focus latitude of lithography and the latitude in the subsequent processing step of the substrate to be processed.
Further, an organic film material having excellent filling/planarizing characteristics is not limited to use as a lower layer film for a multilayer resist, and can be widely used as a planarizing material for manufacturing a semiconductor device, for example, in substrate planarization before patterning by nanoimprint. In addition, although CMP is generally used for global planarization in the semiconductor device manufacturing process, CMP is an expensive process, and is expected as a material for global planarization instead of CMP.
In order to form a planarizing film for planarizing a semiconductor substrate having an uneven surface, a resist underlayer film material containing a polymer obtained by a reaction between an aromatic compound and a compound having a carbon-oxygen double bond such as a carbonyl group has been proposed (patent document 2). However, this material is not sufficient to satisfy the requirements of the most advanced devices such as planarization performance of a wide trench portion in a substrate, and a resist underlayer film material having excellent planarization performance is demanded for a wider substrate structure.
Further, as the structure of the substrate to be processed becomes complicated, studies have been made on the use of a novel material having high electron mobility such as strained silicon, gallium arsenic, etc., or ultra thin film polysilicon controlled to the angstrom unit on the surface of the substrate to be processed, and it is expected that a film can be formed on various shapes and materials of the surface of the substrate to be processed. Therefore, in order to ensure process latitude, not only excellent filling and planarization properties but also film formation that does not depend on the material and shape of the substrate to be processed is an important property.
Documents of the prior art
Patent document
[ patent document 1] Japanese patent application laid-open No. 2004-205685
[ patent document 2] International publication No. 2019/225615
Disclosure of Invention
[ problems to be solved by the invention ]
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compound and a polymer which are capable of forming an organic film which is excellent in heat resistance, filling of a pattern formed on a substrate, and planarization properties, and which has good film-forming properties and adhesion to the substrate, and a composition for forming an organic film containing the compound and/or the polymer. In addition, the invention aims to provide a pattern forming method using the composition.
[ means for solving problems ]
In order to solve the above problems, the present invention provides a composition for forming an organic film, comprising an organic film-forming material represented by the following general formula and an organic solvent.
[ solution 1]
Figure BDA0003865932440000051
(in the formula, R 1 Is a hydrogen atom, an allyl group, or a propargyl group, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms; each V independently represents a hydrogen atom or a linking moiety. )
Such a composition for forming an organic film can form an organic film that is excellent in heat resistance, filling of a pattern formed on a substrate, and planarization properties, and that has good film-forming properties and adhesion to a substrate.
In this case, the organic film-forming material may be a compound represented by the following general formula (1).
[ solution 2]
Figure BDA0003865932440000061
(in the above general formula (1), R 1 、R 2 M, n, l, k, W are as defined above. )
The compound of the present invention represented by the above general formula (1) is excellent in heat resistance and solubility, and therefore can be used as an organic film material using a monomer compound, and is excellent in thermal fluidity as compared with a high molecular weight material, and therefore, when the organic film is used as a resist underlayer film, the compound is also excellent in filling/planarizing characteristics for a pattern substrate. Further, since the molecule has a cyclic amide structure, adhesion to a substrate, film formation properties, and the like can be improved without impairing heat resistance. Further, by appropriately selecting the connecting portion represented by W, it is possible to adjust the performance in accordance with various physical properties required when the organic film is used as a resist underlayer film, such as optical properties and etching resistance.
The compound represented by the above general formula (1) is preferably a compound represented by the following general formula (2).
[ solution 3]
Figure BDA0003865932440000062
(in the above general formula (2), R 1 W and n are the same as above. )
By introducing such a structure, thermal fluidity can be improved, and landfill/planarization performance can be improved.
Further, the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene in gel permeation chromatography of the above compound is preferably 1.00. Ltoreq. Mw/Mn. Ltoreq.1.10.
By controlling the Mw/Mn of the compound for an organic film-forming composition within such a range, an organic film excellent in filling characteristics and flatness can be formed.
In the present invention, the organic film-forming material may be a polymer having a repeating unit represented by the following general formula (3).
[ solution 4]
Figure BDA0003865932440000071
(R in the above general formula (3) 1 、R 2 W, n, m, L and k are the same as above, and L is a C1-40 organic group having a valence of 2. )
By using the polymer having such a repeating unit, a dense organic film having improved curability without deterioration in etching resistance can be formed, and an organic film forming composition excellent in film formation regardless of the substrate material and shape is obtained.
In this case, the polymer is preferably a polymer having a repeating unit represented by the following general formula (4).
[ solution 5]
Figure BDA0003865932440000081
(in the above general formula (4), R 1 W, L and n are the same as above. )
By using a polymer having such a repeating unit, handling properties such as solubility in an organic solvent can be improved.
Further, L is preferably a 2-valent organic group represented by the following general formula (5).
[ solution 6]
Figure BDA0003865932440000082
(in the above general formula (5), R 3 Is a hydrogen atom or an aromatic ring-containing organic group having 1 to 20 carbon atoms, and the dotted line represents an atomic bond. )
By constituting the repeating unit with such a linking group, properties such as curability and etching resistance can be improved.
The weight average molecular weight of the polymer is preferably 1000 to 5000.
If the composition for forming an organic film contains a polymer having a weight average molecular weight in such a range, the composition for forming an organic film can suppress the emission of gas during baking without impairing the solubility in an organic solvent.
In the present invention, the organic film-forming material may contain 1 or more species selected from the group consisting of a compound represented by the following general formula (1) and a polymer having a repeating unit represented by the following general formula (3).
[ solution 7]
Figure BDA0003865932440000091
(in the above general formula (1), R 1 、R 2 M, n, l, k and W are the same as above. )
[ solution 8]
Figure BDA0003865932440000092
(R in the above general formula (3) 1 、R 2 、WN, m, L and k are the same as above, and L is a C1-40 organic group having a valence of 2. )
In the case of such a mixture, various physical properties required for using an organic film, such as filling/planarization characteristics and a gas dissipated due to a sublimate, can be adjusted to an appropriate range.
The organic solvent is preferably a mixture of 1 or more organic solvents having a boiling point of less than 180 ℃ and 1 or more organic solvents having a boiling point of less than 180 ℃.
If the organic solvent is the mixture, the organic film-forming composition can be an organic film-forming composition having both high burying/planarizing characteristics by imparting thermal fluidity to the organic film by adding a high boiling point solvent to the compound and/or the polymer.
Further, the organic film-forming composition preferably contains 1 or more of a surfactant and a plasticizer.
The organic film-forming composition containing the additive is more excellent in coatability and filling/planarizing properties.
Further, the present invention provides a pattern forming method, comprising: the method for forming a pattern on a work object includes the steps of forming an organic film on the work object using the composition for forming an organic film, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film on which the pattern is transferred as a mask, and further forming a pattern on the work object by etching using the organic film on which the pattern is transferred as a mask.
By the above-described pattern forming method by the 3-layer resist process, a fine pattern can be formed with high accuracy on a workpiece.
Further, the present invention provides a pattern forming method, comprising:
forming an organic film on a workpiece using the organic film forming composition, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming an organic anti-reflective coating (BARC) on the silicon-containing resist intermediate film, forming a resist upper film on the BARC using a photoresist composition to form a 4-layer film structure, forming a circuit pattern on the resist upper film, transferring the pattern of the patterned resist upper film to the BARC film and the silicon-containing resist intermediate film by etching using the BARC film as a mask, transferring the pattern of the transferred pattern of the silicon-containing resist intermediate film to the organic film by etching using the BARC film as a mask, and further etching the workpiece using the organic film of the transferred pattern as a mask to form a pattern on the workpiece.
By the pattern forming method by the 4-layer resist processing, a fine pattern can be formed on a workpiece with higher accuracy.
Further, the present invention provides a pattern forming method, comprising:
the method for forming a pattern on a work piece includes the steps of forming an organic film on the work piece using the composition for forming an organic film, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition, forming a circuit pattern on the resist upper layer film, etching the inorganic hard mask using the patterned resist upper layer film as a mask, etching the organic film using the patterned inorganic hard mask as a mask, and etching the work piece using the patterned organic film as a mask to form a pattern on the work piece.
By the above-described pattern forming method by the 3-layer resist process, a fine pattern can be formed with high accuracy on a workpiece.
Further, the present invention provides a pattern forming method, comprising:
forming an organic film on a workpiece using the composition for forming an organic film, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a BARC on the inorganic hard mask, forming a resist upper layer film on the BARC using a photoresist composition to form a 4-layer film structure, forming a circuit pattern on the resist upper layer film, etching the BARC film and the inorganic hard mask using the patterned resist upper layer film as a mask, etching the organic film using the patterned inorganic hard mask as a mask, and further etching the workpiece using the patterned organic film as a mask to form a pattern on the workpiece.
By the pattern forming method by the 4-layer resist process, a fine pattern can be formed on a workpiece with high accuracy.
In this case, the inorganic hard mask is preferably formed by a CVD method or an ALD method.
When the inorganic hard mask is formed by CVD or ALD, a fine pattern can be formed on a workpiece with higher accuracy.
The above-mentioned resist upper layer film is preferably patterned by photolithography with a wavelength of 10nm to 300nm, direct drawing with an electron beam, nanoimprinting, or a combination thereof
When the above method is used as a method for forming a circuit pattern on the resist upper layer film, a fine pattern can be formed on a workpiece with higher accuracy.
In the above-mentioned pattern forming method, exposure and development for forming a circuit pattern on the resist upper layer film are performed, and the development is alkali development or development using an organic solvent.
As a developing method, alkali development or development using an organic solvent is used, whereby a fine pattern can be formed on a workpiece with higher accuracy.
The workpiece is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.
In the present invention, the above-described object to be processed can be used, for example.
In this case, the metal is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.
These can be used as the above metal. In this manner, when the material for forming an organic film of the present invention is used for patterning, the pattern of the upper layer photoresist can be transferred to the object to be processed with high precision.
Further, the present invention provides a compound represented by the following general formula (1).
[ solution 9]
Figure BDA0003865932440000131
(in the general formula (1), R 1 Is a hydrogen atom, allyl, or propargyl, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms. )
The compound represented by the above general formula (1) can provide a compound for an organic film-forming composition which can form an organic film excellent in heat resistance, filling/planarizing properties, and film-forming properties.
In this case, the compound is preferably a compound represented by the following general formula (2).
[ solution 10]
Figure BDA0003865932440000141
(in the above general formula (2), R 1 W and n are the same as above. )
Such a compound can further improve the filling/planarization properties of the compound for an organic film-forming composition.
The present invention also provides a polymer having a repeating unit represented by the following general formula (3).
[ solution 11]
Figure BDA0003865932440000142
(in the general formula (3), R 1 Is a hydrogen atom, an allyl group, or a propargyl group, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms; l is a C1-40 2-valent organic group. )
The polymer represented by the above general formula (3) can provide a polymer for an organic film-forming composition which can form an organic film having excellent curability.
In this case, a polymer having a repeating unit represented by the following general formula (4) is preferable.
[ solution 12]
Figure BDA0003865932440000151
(in the above general formula (4), R 1 W, L and n are the same as above. )
The polymer having the above repeating unit is a polymer for an organic film-forming composition having excellent solubility in a solvent.
Further, L is preferably a 2-valent organic group represented by the following general formula (5).
[ solution 13]
Figure BDA0003865932440000152
(in the above general formula (5), R 3 Is a hydrogen atom or an aromatic ring-containing organic group having 1 to 20 carbon atoms, and the dotted line represents an atomic bond)
By introducing such a linking group L, various physical properties such as curability and etching resistance of the polymer can be improved.
[ Effect of the invention ]
As described above, the compound or polymer of the present invention can be used to form an organic film excellent in heat resistance, filling/planarizing properties and film forming properties. The composition for forming an organic film containing the compound and/or the polymer can have various properties such as heat resistance and filling/planarizing properties, and is a useful material for forming an organic film that can be formed without depending on a process substrate. Therefore, the composition is extremely useful as a composition for forming an organic film or a planarization material for producing a semiconductor device in a multilayer resist process such as a 2-layer resist process, a 3-layer resist process using a silicon-containing resist intermediate film, or a 4-layer resist process using a silicon-containing resist intermediate film and an organic anti-reflective film. In addition, according to the pattern forming method of the present invention, a fine pattern can be formed with high accuracy on a workpiece in a multilayer resist process.
Drawings
FIG. 1 (A) to (F) are explanatory views of an example of a pattern forming method by a 3-layer resist process of the present invention.
[ FIG. 2] (G) to (I) are explanatory views of the method for evaluating the filling characteristics in examples and comparative examples.
FIG. 3 (J) and (K) are explanatory views of the planarization characteristic evaluation methods in the examples and comparative examples.
FIG. 4 is an explanatory view showing a method of measuring adhesion in examples and comparative examples.
Detailed Description
As described above, in the fine patterning process using the multilayer resist method in the semiconductor device manufacturing process, there are a composition for forming an organic film which is capable of forming an organic film excellent in film forming property and flatness even on a workpiece (substrate to be processed) having a portion which is particularly difficult to be planarized, such as a wide trench structure (wide trench) having a wide width, a pattern forming method using the composition for forming an organic film, and a compound and a polymer suitable for the composition for forming an organic film.
The present inventors have found that the compound or polymer having a main skeleton formed by a specific heterocyclic structure of the present invention is useful for forming an organic film having excellent filling/planarizing properties, and have completed the present invention.
That is, the present invention is a composition for forming an organic film, comprising an organic film-forming material represented by the following general formula and an organic solvent.
[ solution 14]
Figure BDA0003865932440000171
(in the formula, R 1 Is a hydrogen atom, an allyl group, or a propargyl group, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms; each V independently represents a hydrogen atom or a linking moiety. )
The embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
[ composition for Forming organic film ]
The composition for forming an organic film of the present invention contains an organic film-forming material represented by a specific general formula described below and an organic solvent.
The organic film-forming composition may contain an organic film-forming material represented by the general formula and an organic solvent, and may contain an additive such as a surfactant or a plasticizer as required. The components contained in the composition of the present invention will be described below.
[ organic film Forming Material ]
The composition for forming an organic film of the present invention is characterized by containing an organic film-forming material represented by the following general formula.
[ solution 15]
Figure BDA0003865932440000181
(in the formula, R 1 Is a hydrogen atom, an allyl group, or a propargyl group, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms; each V independently represents a hydrogen atom or a linking moiety. )
R in the above formula 1 Is a hydrogen atom, an allyl group, or a propargyl group. From the viewpoint of thermosetting properties, a hydrogen atom or a propargyl group is preferable, and from the viewpoint of imparting thermal fluidity, a propargyl group is particularly preferable.
R 2 Represents a halogen atom such as nitro, fluorine or chlorine, an alkyloxy group having 1 to 4 carbon atoms such as hydroxy, methoxy or ethoxy, an alkynyloxy group having 2 to 4 carbon atoms such as propargyloxy, an alkenyloxy group having 2 to 4 carbon atoms such as allyloxy, a straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms such as methyl, isobutyl or cyclohexyl, a trifluoromethyl group or a trifluoromethyloxy group.
m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and l =1 means that the aromatic rings form a cyclic ether structure with each other. In addition, n and l satisfy the relationship of 1. Ltoreq. N + l. Ltoreq.3. k represents an integer of 0 to 2. m is preferably 0, l is preferably 0, k is preferably 0.
In the above general formula, W is a 2-valent organic group having 1 to 40 carbon atoms, preferably a 2-valent organic group having 2 to 30 carbon atoms, and specifically, the following structures and the like can be exemplified. Among these, alkylene is preferable from the viewpoint of easiness of obtaining raw materials and imparting thermal fluidity.
[ solution 16]
Figure BDA0003865932440000191
(dotted line represents an atomic bond)
V represents each independently a hydrogen atom or a linking moiety. When all V are hydrogen atoms (having no linking portion), the organic film-forming material represented by the above general formula is a monomolecular compound corresponding to the compound represented by the following general formula (1). When V is a linking moiety, the organic film-forming material is a polymer. The linking moiety is a moiety in which the structures represented by the above general formulae are linked to each other, and examples thereof include a single bond and a linking group L described later. That is, the polymer includes a polymer having a repeating unit represented by the following general formula (3).
The organic film-forming material may be a compound represented by general formula (1) described below, a compound represented by general formula (2) (hereinafter, these compounds are also referred to as "compound for an organic film-forming composition"), a polymer having a repeating unit represented by general formula (3) described below, or a polymer having a repeating unit represented by general formula (4) (hereinafter, these polymers are also referred to as "polymer for an organic film-forming composition"). The organic film-forming material may contain 1 or more species selected from the group consisting of the compound represented by the general formula (1) and the polymer having the repeating unit represented by the general formula (3).
< Compound for organic film Forming composition >
The composition for forming an organic film of the present invention may contain a compound represented by the following general formula (1) (compound for forming an organic film) as an organic film-forming material.
[ chemical formula 17]
Figure BDA0003865932440000201
(in the above general formula (1), R 1 、R 2 M, n, l, k, W are as defined above. )
W in the general formula (1) is a 2-valent organic group having 1 to 40 carbon atoms, preferably a 2-valent organic group having 2 to 30 carbon atoms, and specifically, the above structure and the like can be exemplified. Among these, alkylene is preferable from the viewpoint of easiness of obtaining raw materials and imparting thermal fluidity.
R in the above general formula (1) 1 Is a hydrogen atom, an allyl group, or a propargyl group. From the viewpoint of thermosetting properties, a hydrogen atom or a propargyl group is preferable, and from the viewpoint of imparting thermal fluidity, a propargyl group is particularly preferable.
R 2 Represents a halogen atom such as nitro, fluorine or chlorine, an alkyloxy group having 1 to 4 carbon atoms such as hydroxy, methoxy or ethoxy, an alkynyloxy group having 2 to 4 carbon atoms such as propargyloxy, an alkenyloxy group having 2 to 4 carbon atoms such as allyloxy, a straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms such as methyl, isobutyl or cyclohexyl, a trifluoromethyl group or a trifluoromethyloxy group.
m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and l =1 means that the aromatic rings form a cyclic ether structure with each other. In addition, n and l satisfy the relationship of 1. Ltoreq. N + l. Ltoreq.3. k represents an integer of 0 to 2. m is preferably 0, l is preferably 0, k is preferably 0.
Specific examples of the general formula (1) include the following, R 1 、R 2 W and k are the same as above.
[ formula 18]
Figure BDA0003865932440000221
Further, the compound is preferably a compound represented by the following general formula (2).
[ solution 19]
Figure BDA0003865932440000222
Specific examples of the compound (2) in the above general formula include the following compounds, and among these compounds, a compound having a propargyl group as a substituent is particularly preferable in view of thermal fluidity and curability. W in the following general formula is as defined above.
[ solution 20]
Figure BDA0003865932440000231
Further, the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene of the compound represented by the general formula (1) by gel permeation chromatography is preferably 1.00. Ltoreq. Mw/Mn. Ltoreq.1.10. In the definition, mw/Mn is 1.00 in the case of a monomolecular compound, but the measured value may exceed 1.00 due to the separability of gel permeation chromatography. Generally, a polymer having a repeating unit is extremely difficult to approach Mw/Mn =1.00 without using a special polymerization method, and has a Mw distribution and a value of Mw/Mn exceeding 1. In the present invention, 1.00. Ltoreq. Mw/Mn. Ltoreq.1.10 is defined as an index representing monomolecularity for distinguishing a monomolecular compound from a polymer.
By controlling the Mw/Mn of the compound for an organic film-forming composition within such a range, an organic film excellent in filling characteristics and flatness can be formed.
The compound of the present invention has a structure containing a large amount of aromatic rings, and therefore, is excellent in heat resistance and etching resistance, and can be used as an organic film-forming compound in combination with a substituent imparting fluidity and curability, a heterocyclic structure imparting film-forming properties and adhesion, or a linking structure for further improving fluidity.
[ Process for producing Compound ]
As an example of the method for producing the compound represented by the general formula (1) of the present invention, there can be exemplified a process (STEP 1) in which a compound represented by X-W-X having 2 leaving groups X and an indole-2, 3-dione are used as raw materials to obtain a bis (indole-2, 3-dione) as an intermediate by a substitution reaction using a base catalyst, and then a compound having OR 1 A STEP (STEP 2) of obtaining a product by a dehydration condensation reaction using an acid catalyst, wherein benzene or a naphthalene as a substituent is used as a raw material. The reactions used in STEP1 and STEP2 can be used alone or in combination of 2 or more kinds of raw materials, and these can be appropriately selected and combined according to the desired characteristics.
[ solution 21]
Figure BDA0003865932440000251
(R 1 、R 2 W, n, m, l and k are the same as above, and X is halide, tosylate or mesylate. )
Examples of the base catalyst for the reaction of bis (indole-2, 3-dione) compounds to obtain intermediates shown in STEP1 include inorganic base compounds such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride and potassium phosphate, and organic amine compounds such as triethylamine, pyridine and N-methylmorpholine, and these compounds may be used alone or in combination of 2 or more. The amount of the catalyst to be used is, for example, in the range of 0.1 to 20 mol, preferably 0.2 to 10 mol, based on the mole number of indole-2, 3-diones as a raw material.
The solvent used in this case is not particularly limited as long as it is inactive in the above reaction, and for example, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, aromatic solvents such as benzene, toluene and xylene, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and water can be used alone or in a mixture thereof. These solvents can be used in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from-50 ℃ to about the boiling point of the solvent, more preferably from room temperature to 150 ℃. The reaction time is suitably selected from 0.1 to 100 hours.
As the reaction method, there are a method of adding indole-2, 3-dione and X-W-X compounds together into a solvent, a method of adding indole-2, 3-dione and X-W-X compounds dropwise separately or by mixing, dispersing or dissolving them, and a method of adding indole-2, 3-dione and X-W-X compounds dropwise after dispersing or dissolving them in a solvent and then adding them dropwise after dispersing or dissolving them in another solvent. In addition, in the indole-2, 3-two ketone, X-W-X compounds with a plurality of cases, can be mixed in advance and the reaction method, also can make the respective order reaction. When a catalyst is used, there may be mentioned a method of adding the indole-2, 3-diones or compounds represented by X-W-X together, a method of dispersing or dissolving the catalyst in advance and then adding it dropwise, and the like. The bis (indole-2, 3-dione) compound as the intermediate obtained can be recovered as a powder by keeping the reaction solution in a state of continuing the dehydration condensation reaction of STEP2, or by diluting the reaction solution to an organic solvent to remove unreacted raw materials, catalysts and the like present in the reaction intermediate system, and then separating and washing or precipitating crystals from a poor solvent.
Examples of the acid catalyst used in the dehydration condensation reaction shown in STEP2 include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acid, organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid, lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) isopropoxide, and titanium (IV) oxide. The amount of the catalyst to be used is in the range of 0.1 to 20 mol, preferably 0.2 to 10 mol, based on the mol number of the bis (indole-2, 3-dione) compound as an intermediate.
The solvent to be used is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether, ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and 1, 4-dioxane, chlorine-based solvents such as methylene chloride, chloroform, dichloroethane and trichloroethylene, hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene, nitriles such as acetonitrile, ketones such as acetone, ethyl methyl ketone and isobutyl methyl ketone, esters such as ethyl acetate, N-butyl acetate and propylene glycol methyl ether acetate, and aprotic polar solvents such as dimethyl sulfoxide, N-dimethylformamide and hexamethylphosphoric triamide, which may be used alone or in combination of 2 or more. These solvents can be used in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from-50 ℃ to about the boiling point of the solvent, more preferably from room temperature to 150 ℃. The reaction time is suitably selected from 0.1 to 100 hours.
As a reaction method, there are a method of adding bis (indole-2, 3-dione), benzene or naphthalene together with an acid catalyst as a catalyst, a method of dispersing or dissolving bis (indole-2, 3-dione), benzene or naphthalene and then adding the catalyst once or several times or diluting with a solvent and dropping, a method of dispersing or dissolving the catalyst and then adding bis (indole-2, 3-dione), benzene or naphthalene once or several times, respectively, or a method of diluting with a solvent and dropping. In this case, depending on the reactivity of benzene or naphthalene, it is preferable to use 2 moles or more of benzene or naphthalene when 1 mole of bis (indole-2, 3-dione) is used. After the completion of the reaction, the reaction mixture is diluted with an organic solvent to remove the catalyst used in the reaction, and then subjected to liquid separation and washing to recover the desired product.
The organic solvent used in this case is not particularly limited as long as it can dissolve the desired product and can be separated into 2 layers when mixed with water, and examples thereof include hydrocarbons such as hexane, heptane, benzene, toluene, xylene, etc., esters such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, etc., ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, methyl isobutyl ketone, etc., ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, ethyl cyclopentyl methyl ether, etc., chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, trichloroethylene, etc., and mixtures thereof. The cleaning water used in this case may be deionized water or ultrapure water. The number of washing may be 1 or more, but the washing effect is not necessarily obtained even if the washing is 10 or more times, and is preferably about 1 to 5 times.
In the liquid separation cleaning, cleaning with an alkaline aqueous solution is performed to remove acidic components in the system. Specific examples of the base include hydroxides of alkali metals, carbonates of alkali metals, hydroxides of alkaline earth metals, carbonates of alkaline earth metals, ammonia, and organic ammonium.
Further, the cleaning may be performed with an acidic aqueous solution in order to remove metal impurities or alkali components in the system at the time of the liquid separation cleaning. Specific examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and heteropoly acid, and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.
The liquid separation washing with the alkaline aqueous solution or the acidic aqueous solution may be performed alone or in combination. In view of removing metal impurities, the liquid separation and washing is preferably performed in the order of an alkaline aqueous solution and an acidic aqueous solution.
After the above-mentioned liquid separation washing with an alkaline aqueous solution or an acidic aqueous solution, washing with neutral water may be performed. The number of washing may be 1 or more, preferably about 1 to 5. The neutral water may be deionized water or ultrapure water. The number of washing times may be 1 or more, but when the number is small, the alkali component and the acid component may not be removed. The washing time is preferably about 1 to 5 times, since the washing effect is not always obtained when the washing is performed 10 times or more.
Further, the reaction product after the liquid separation operation can be recovered as a powder by concentrating and drying or crystallizing the solvent under reduced pressure or normal pressure, and can be made into a solution state with an appropriate concentration for the purpose of improving the operability in the preparation of the composition for forming an organic film. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. Such a concentration is economically preferable because the viscosity is not likely to increase and the workability is prevented from being impaired, and the amount of the solvent does not become too large.
The solvent in this case is not particularly limited as long as it can dissolve the compound, and specific examples thereof include ketones such as cyclohexanone and methyl-2-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol and 1-ethoxy-2-propanol, and ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether; propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and other esters, which can be used alone or in combination of 2 or more.
< Polymer for organic film Forming composition >
The composition for forming an organic film of the present invention may contain a polymer having a repeating unit represented by the following general formula (3) (polymer for forming an organic film), preferably a polymer having a repeating unit represented by the general formula (4).
[ solution 22]
Figure BDA0003865932440000291
(R in the above general formula (3) 1 、R 2 W, n, m, L and k are the same as above, and L is a C1-40 organic group having a valence of 2. )
These polymers obtained by using the compound represented by the above general formula (1) are excellent in heat resistance, flatness and thermosetting properties. Further, since the polymer having a repeating unit is not a monomer (monomolecular compound), the amount of a gas component to be dissipated is small, and since the polymer has a molecular weight distribution, crystallinity is moderate, and improvement in film forming properties is expected.
L of the linking group constituting the repeating units of the general formulae (3) and (4) is a 2-valent organic group having 1 to 40 carbon atoms, and specific examples thereof include the following.
[ solution 23]
Figure BDA0003865932440000311
/>
(dotted line represents an atomic bond)
Further, L is preferably represented by the following general formula (5).
[ solution 24]
Figure BDA0003865932440000321
(in the above general formula (5), R 3 Is a hydrogen atom or an aromatic ring-containing organic group having 1 to 20 carbon atoms, and the dotted line represents an atomic bond. )
Specific examples of the general formula (5) include the following, and methylene, that is, R is preferable in consideration of easiness of obtaining the raw material 3 Is a hydrogen atom.
[ solution 25]
Figure BDA0003865932440000322
(dotted line represents an atomic bond)
The Mw (weight average molecular weight) of the above-mentioned polymer is preferably 1000 to 5000, more preferably 1000 to 4000. The molecular weight can be determined as a weight average molecular weight (Mw) in terms of polystyrene by Gel Permeation Chromatography (GPC) using tetrahydrofuran as an eluent.
Such a molecular weight range ensures solubility in an organic solvent and suppresses sublimation generated during baking. Further, since the polymer for the organic film-forming composition has good thermal fluidity, when it is blended into a material, it can form an organic film in which not only the fine structure formed on the substrate is favorably filled but also the entire substrate is flat.
[ method for producing Polymer ]
The polymer used in the organic film-forming composition of the present invention can be obtained by a polycondensation reaction of a compound represented by the general formula (1) with an aldehyde, a ketone, or a benzyl alcohol. R in the formula 1 、R 2 W, n, m, l, k are the same as (R) 4 、R 5 Wherein either or both of them are hydrogen atoms means polycondensation with aldehyde, the other means polycondensation with ketone, and AR means an aromatic compound, -CH, such as benzene or naphthalene 2 The substituent represented by-OH is a substituent of an aromatic ring.)。
[ solution 26]
Figure BDA0003865932440000331
/>
The condensation polymerization reaction as described above can be usually obtained in an organic solvent in the presence of an acid catalyst at room temperature or, as required, under cooling or heating. The acid catalyst to be used includes inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and heteropoly acid, organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid, lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) isopropoxide and titanium (IV) oxide.
Examples of the solvent to be used include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether, ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and 1, 4-dioxane, chlorine-based solvents such as methylene chloride, chloroform, dichloroethane and trichloroethylene, hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene, nitriles such as acetonitrile, ketones such as acetone, ethyl methyl ketone and isobutyl methyl ketone, esters such as ethyl acetate, N-butyl acetate and propylene glycol methyl ether acetate, and aprotic polar solvents such as dimethyl sulfoxide, N-dimethylformamide and hexamethylphosphoric triamide, and these solvents can be used alone or in combination of 2 or more.
The reaction method and the method for recovering a polymer can be carried out by the methods described in the method for producing a compound represented by the above general formula (1).
[ Another method for producing Compound and Polymer ]
In addition, in this applicationR of the compound represented by the above general formula (1) or the polymer represented by the general formula (3) used in the composition for forming an organic film 1 In the case where the hydrogen atom is other than hydrogen atom, another method of the production method includes the following steps: a STEP (STEP 1) of obtaining an intermediate by a dehydration condensation reaction using an acid catalyst using bis (indole-2, 3-dione) and benzene or naphthalene having a hydroxyl group, i.e., so-called phenol or naphthol as raw materials. The monomolecular compound can be obtained by a method having the following steps: using conversion of hydroxy groups to OR 1 R with a leaving group X 1 A substitution reaction (STEP 2-1) using a base catalyst and a raw material represented by X; the polymer can be obtained by a process having the following steps: the condensation polymerization reaction (STEP 2-2) using the compound obtained in (STEP 1) is followed by conversion of the hydroxyl group to OR 1 R with a leaving group X 1 The substitution reaction (STEP 3) is carried out using a base catalyst and a starting material represented by-X. In this case, R 1 X can be used alone OR in combination of 2 OR more, and the hydroxyl group and OR can be controlled by controlling the reaction rate 1 The ratio of (a) to (b). By introducing a polar structure such as a hydroxyl group in part, film forming properties and adhesion of the film to the substrate can be controlled.
[ solution 27]
Figure BDA0003865932440000351
(R 1 、R 2 W, X, n, m, l, k are as described above. )
The dehydration condensation reaction of (STEP 1) and the polycondensation reaction of (STEP 2-2) can be carried out by the methods described in the methods for producing the compound (1) and the polymer (3), respectively.
The reaction method and the method for recovering the compound or polymer can be carried out by the methods described in the method for producing the compound represented by the above general formula (1).
Examples of the base catalyst used in the substitution reaction of (STEP 2-1) and (STEP 3) include inorganic basic compounds such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride and potassium phosphate, and organic amine compounds such as triethylamine, pyridine and N-methylmorpholine, and these can be used alone or in combination of 2 or more.
The solvent used in this case is not particularly limited as long as it is inactive in the above reaction, and examples thereof include ether solvents such as diethyl ether, tetrahydrofuran and dioxane, aromatic solvents such as benzene, toluene and xylene, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and water, and these solvents may be used alone or in combination.
The reaction method and the method for recovering the compound or the polymer can be carried out by the methods described in the method for producing the compound represented by the above general formula (1).
In the preparation of the compound or polymer used in the composition for forming an organic film obtained by the method, a plurality of various halides, tosylates and mesylates can be used alone or in combination in accordance with the desired performance. For example, aromatic ring structures having a side chain structure contributing to improvement of planarization characteristics, rigidity contributing to etching resistance and heat resistance, and the like can be combined at an arbitrary ratio. Therefore, the composition for forming an organic film using these compounds or polymers can have both of the filling/planarizing property and the etching resistance at a high level.
As described above, the compound or polymer for an organic film-forming composition of the present invention can provide a compound or polymer that can give an organic film-forming composition exhibiting high etching resistance and excellent distortion resistance.
[ Compound and/or Polymer for organic film-Forming composition ]
In the organic film-forming composition of the present invention containing the compound and/or polymer for an organic film-forming composition and an organic solvent as an organic film-forming material, the compound or polymer for an organic film-forming composition may be used alone or in combination of plural kinds.
In the present invention, the organic film-forming composition preferably contains 1 or more species selected from the group consisting of the compounds and polymers for use in the organic film-forming composition, and more specifically, the organic film-forming material preferably contains 1 or more species selected from the group consisting of the compounds represented by the general formula (1) and the polymers having the repeating unit represented by the general formula (3).
In the case of the mixture as described above, various physical properties required when an organic film is used, such as filling/planarization characteristics and a gas dissipated from a sublimate, can be adjusted to an appropriate range.
[ organic solvent ]
The organic solvent that can be used in the organic film-forming material of the present invention is not particularly limited as long as it dissolves the compound and/or the polymer (base polymer), and if contained, a surfactant, a crosslinking agent, other additives, and the like, which will be described later. Specifically, solvents having a boiling point of less than 180 ℃ such as the solvents described in paragraphs [0091] to [0092] in Japanese patent application laid-open No. 2007-199653 can be used. Among them, propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone and a mixture of 2 or more of these are preferably used. The amount of the organic solvent to be blended is preferably 200 to 10,000 parts, more preferably 300 to 5,000 parts, based on 100 parts of the compound (A) and/or the polymer (A).
Such a composition for forming an organic film can be applied by spin coating, and further contains the compound and/or polymer for forming an organic film of the present invention as described above, and thus provides a composition for forming an organic film having both heat resistance and high burying/planarizing characteristics.
In the composition for forming an organic film of the present invention, a high boiling point solvent having a boiling point of 180 ℃ or higher (a mixture of a solvent having a boiling point of less than 180 ℃ and a solvent having a boiling point of 180 ℃ or higher) may be added as the organic solvent to the solvent having a boiling point of less than 180 ℃. <xnotran> , / , , , , , , , , 1- ,2- ,1- ,1- ,1- , ,1,2- ,1,3- ,2,4- ,2- -2,4- ,2,5- ,2,4- ,2- -1,3- , , , , , , , , -2- , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1, 4-butane diol diacetate, 1, 3-butane diol diacetate, 1, 6-hexane diol diacetate, triethylene glycol diacetate, γ -butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, and the like, and these may be used alone or in admixture thereof.
The boiling point of the high boiling point solvent is suitably selected depending on the temperature at which the organic film-forming composition is heat-treated, and the boiling point of the high boiling point solvent to be added is preferably from 180 to 300 ℃, more preferably from 200 to 300 ℃. If the boiling point is too low, there is no fear that the volatilization rate at the time of baking (heat treatment) is too high because of too low boiling point, and thus sufficient thermal fluidity can be obtained. In addition, if the boiling point is such a boiling point, the boiling point is not too high and the film does not volatilize and remain in the film after baking, and therefore there is no possibility that the film properties such as etching resistance are adversely affected.
When the high boiling point solvent is used, the amount of the high boiling point solvent to be added is preferably 1 to 30 parts by mass per 100 parts by mass of the solvent having a boiling point of less than 180 ℃. Such a blending amount can impart sufficient thermal fluidity during baking, and does not remain in the film to cause deterioration of film properties such as etching resistance.
Such an organic film-forming composition is used to impart thermal fluidity by adding a high-boiling point solvent to the organic film-forming composition, and thus provides an organic film-forming composition having both high burying and leveling properties.
[ acid generators ]
In the organic film forming composition of the present invention, an acid generator may be added to further accelerate the curing reaction. The acid generator may be any one of an acid generator that generates an acid by thermal decomposition and an acid generator that generates an acid by light irradiation. Specifically, the materials described in paragraphs [0061] to [0085] of jp 2007-199653 a can be added, but the materials are not limited thereto.
The acid generator can be used alone 1 or a combination of 2 or more. The amount of the acid generator to be added is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, per 100 parts of the compound and/or the polymer.
[ surfactant ]
In the composition for forming an organic film of the present invention, a surfactant may be added to improve the coatability by spin coating. As the surfactant, for example, the surfactants described in [0142] to [0147] in Japanese patent laid-open publication No. 2009-269953 can be used. The amount of the surfactant added is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, per 100 parts of the compound and/or the polymer.
In the present invention, the organic film-forming composition preferably further contains 1 or more of a surfactant and a plasticizer.
[ crosslinking agent ]
In addition, in the composition for forming an organic film of the present invention, a crosslinking agent may be added in order to improve the hardening property and further suppress intermixing with the upper layer film. The crosslinking agent is not particularly limited, and known crosslinking agents of various systems can be widely used. Examples thereof include a methylol or alkoxymethyl type crosslinking agent of polynuclear phenols, a melamine-based crosslinking agent, a Glycoluril (Glycoluril) -based crosslinking agent, a benzoguanamine-based crosslinking agent, a urea-based crosslinking agent, a β -hydroxyalkylamide-based crosslinking agent, an isocyanurate-based crosslinking agent, an aziridine-based crosslinking agent, an oxazoline-based crosslinking agent, and an epoxy-based crosslinking agent. The amount of the crosslinking agent added is preferably 1 to 100 parts, more preferably 5 to 50 parts, per 100 parts of the compound and/or the polymer.
Specific examples of the melamine-based crosslinking agent include hexamethoxy methylated melamine, hexabutoxy methylated melamine, alkoxy and/or hydroxy substituted products thereof, and partial self-condensates thereof. Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and/or hydroxy-substituted products thereof, and partial self-condensates thereof. Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy and/or hydroxy-substituted products thereof, and partial self-condensates thereof. Specific examples of the urea-based crosslinking agent include dimethoxymethylated dimethoxyethylene urea, alkoxy and/or hydroxy-substituted compounds thereof, and partial self-condensates thereof. Specific examples of the β -hydroxyalkylamide-based crosslinking agent include N, N' -tetrakis (2-hydroxyethyl) adipate. Specific examples of the isocyanurate-based crosslinking agent include triallyl isocyanurate and triallyl isocyanurate. Specific examples of the aziridine-based crosslinking agent include 4,4' -bis (ethyleneiminocarbonylamino) diphenylmethane and 2, 2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate ]. Specific examples of the oxazoline-based crosslinking agent include 2,2 '-isopropylidenebis (4-benzyl-2-oxazoline), 2' -isopropylidenebis (4-phenyl-2-oxazoline), 2 '-methylenebis 4, 5-diphenyl-2-oxazoline, 2' -methylenebis-4-phenyl-2-oxazoline, 2 '-methylenebis-4-tert-butyl-2-oxazoline, 2' -bis (2-oxazoline), 1, 3-phenylenebis (2-oxazoline), 1, 4-phenylenebis (2-oxazoline), and 2-isopropenyloxazoline copolymers. Specific examples of the epoxy-based crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, poly (glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.
Specific examples of the polynuclear phenol-based crosslinking agent include compounds represented by the following general formula (6).
[ solution 28]
Figure BDA0003865932440000411
(wherein Q is a single bond or a Q-valent hydrocarbon group having 1 to 20 carbon atoms R 6 Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q is an integer of 1 to 5. )
Q is a single bond or a hydrocarbon group having 1 to 20 carbon atoms and a valence of Q. q is an integer of 1 to 5, preferably 2 or 3. Specific examples of Q include those obtained by removing Q hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylcumene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R 6 Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosyl group, and a hydrogen atom or a methyl group is preferable.
Specific examples of the compound represented by the above general formula (6) include the following compounds. Of these, in view of improving the curing properties and the uniformity of the film thickness of the organic film, triphenylol methane, triphenylol ethane, and 1, 1-tris (4-hydroxybenzene) are preferableAlkyl) ethane, and a hexamethoxy methylated form of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene. R 6 As above.
[ solution 29]
Figure BDA0003865932440000431
[ solution 30]
Figure BDA0003865932440000441
[ plasticizers ]
In the organic film-forming composition of the present invention, a plasticizer may be added to improve planarization/filling properties. The plasticizer is not particularly limited, and various known plasticizers can be widely used. Examples thereof include low-molecular-weight compounds such as phthalic acid esters, adipic acid esters, phosphoric acid esters, trimellitic acid esters, and citric acid esters, and polymers such as polyether polymers, polyester polymers, and polyacetal polymers described in Japanese patent application laid-open No. 2013-253227. The plasticizer is preferably added in an amount of 1 to 100 parts, more preferably 5 to 30 parts, based on 100 parts of the compound and/or the polymer.
In the organic film-forming composition of the present invention, as an additive for imparting filling/flattening properties in the same manner as the plasticizer, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer having a weight-loss rate of 40 mass% or more at 30 to 250 ℃ and a weight-average molecular weight of 300 to 200,000 is preferably used. The thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP 1) or (DP 1 a).
[ solution 31]
Figure BDA0003865932440000451
(in the formula, R 7 Is a hydrogen atom or a carbon number 1 which may be substituted30 saturated or unsaturated monovalent organic groups. Y is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms. )
[ solution 32]
Figure BDA0003865932440000452
(in the formula, R 8 Is an alkyl group having 1 to 4 carbon atoms. Z is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms and may have an ether bond. j represents the average number of repeating units and is 3 to 500. )
[ other ingredients ]
The composition for forming an organic film of the present invention may further contain other compounds and polymers. The blending compound or blending polymer is mixed with the composition for forming an organic film of the present invention, and has an effect of improving the film forming property by spin coating and the burying property of a substrate having a step difference.
<xnotran> , , , , ,2,3- ,2,5- ,3,4- ,3,5- ,2,4- ,2,6- ,2,3,5- ,3,4,5- ,2- ,3- ,4- ,2- ,3- ,4- ,3,5- ,2- ,3- ,4- ,4- , ,2- ,4- ,5- , ,4- ,2- ,3- ,2- ,3- ,4- ,2- ,3- ,4- ,2- -5- ,2- -5- , , , ,4,4' - (9H- -9- ) ,2,2 ' -4,4' - (9H- -9- ) ,2,2 ' -4,4' - (9H- -9- ) ,2,2 ' -4,4' - (9H- -9- ) ,2,2 ' -4,4' - (9H- -9- ) , </xnotran> 2,2 '-dimethoxy-4, 4' - (9H-fluoren-9-ylidene) bisphenol, 2,3,2',3' -tetrahydro- (1, 1 ') -spirobiindan-6, 6' -diol, 3 '-tetramethyl-2, 3,2',3 '-tetrahydro- (1, 1') -spirobiindan-6, 6 '-diol, 3',3', 4' -hexamethyl-2, 3,2',3' -tetrahydro- (1, 1 ') -spirobiindan-6, 6' -diol, 2,3,2',3' -tetrahydro- (1, 1 ') -spirobiindan-5, 5' -diol, 5 '-dimethyl-3, 3' -tetramethyl-2, 3,2',3' -tetrahydro- (1, 1 ') -spirobiindan-6, 6' -diol, 1-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, 1, 5-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2, 6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, vinylnaphthalene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorbornane-2-ene, alpha-pinene, beta-pinene, limonene (limonene) and other novolak resins, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, etc, polyvinylcarbazole, polyindene, polyvinylnaphthalene, polynorbornene, polycyclodecene, polycyclododecene, polytriazyclo [2.2.1.0 (2, 6) ] heptane (poly-nortricycle), poly (meth) acrylates and copolymers of these. Further, a naphthol dicyclopentadiene copolymer described in japanese patent application laid-open No. 2004-205685, a fluorene bisphenol novolac resin described in japanese patent application laid-open No. 2005-128509, an ethylene naphthalene copolymer described in japanese patent application laid-open No. 2005-250434, a fullerene having a phenol group described in japanese patent application laid-open No. 2006-227391, a bisphenol compound and the novolac resin described in japanese patent application laid-open No. 2006-293298, a novolac resin of an adamantane phenol compound described in japanese patent application laid-open No. 2006-285095, a bisnaphthol compound and the novolac resin described in japanese patent application laid-open No. 2010-122656, a fullerene resin compound described in japanese patent application laid-open No. 2008-158002, and the like may be blended.
The amount of the compound or polymer to be blended is preferably 0 to 1,000 parts by mass, more preferably 0 to 500 parts by mass, per 100 parts by mass of the organic film-forming composition of the present invention.
Further, the organic film-forming material of the present invention may be used alone in 1 kind or in combination with 2 or more kinds. The organic film-forming material can be used for an organic film material or a planarization material for manufacturing a semiconductor device.
The composition for forming an organic film of the present invention is extremely useful as an organic film material for multilayer resist processing such as 2-layer resist processing, 3-layer resist processing using a silicon-containing intermediate film, and 4-layer resist processing using a silicon-containing inorganic hard mask and an organic anti-reflective film.
(method for Forming organic film)
The present invention provides a method for forming an organic film that functions as an organic film of a multilayer resist film used for lithography or a planarizing film for semiconductor production, using the above composition for forming an organic film.
The organic film forming method using the composition for forming an organic film of the present invention is to coat the composition for forming an organic film on a substrate to be processed by a spin coating method or the like. By using a spin coating method or the like, good filling characteristics can be obtained. After the spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction in order to prevent mixing with the resist upper layer film and the resist intermediate layer film. The baking is preferably carried out at 100 ℃ to 600 ℃ for 10 to 600 seconds, more preferably at 200 ℃ to 500 ℃ for 10 to 300 seconds. Considering the influence on the damage of the device and the deformation of the wafer, the upper limit of the heating temperature in the wafer processing by photolithography is preferably 600 ℃ or less, and more preferably 500 ℃ or less.
In the organic film forming method using the composition for forming an organic film of the present invention, the composition for forming an organic film of the present invention may be applied to a substrate to be processed by the same spin coating method or the like as described above, and the composition for forming an organic film may be fired and cured in an environment having an oxygen concentration of 0.1 vol% or more and 21 vol% or less to form an organic film.
By calcining the organic film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained. The environment during baking may be air, and N may be sealed for reducing oxygen 2 Inert gases such as Ar and He are preferred for preventing oxidation of the organic film. Is composed ofThe oxygen concentration is controlled to prevent oxidation, preferably 1000ppm or less, more preferably 100ppm or less (volume basis). It is preferable that oxidation of the organic film during baking is prevented because absorption does not increase or etching resistance does not decrease.
The organic film forming method using the composition for forming an organic film of the present invention can obtain a flat cured film without regard to the unevenness of the substrate to be processed by the excellent filling and flattening characteristics, and is therefore extremely useful for forming a flat cured film on a substrate to be processed having a structure with a height of 30nm or more or a level difference.
The thickness of the organic film, such as the organic film or the planarizing film for manufacturing a semiconductor device, is appropriately selected, and is preferably 30 to 20,000nm, particularly preferably 50 to 15,000nm.
(Pattern Forming method)
The present invention provides a method for forming a pattern on a workpiece, the method comprising at least the steps of: the method for forming a pattern on a work includes the steps of forming an organic film on the work using the composition for forming an organic film, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask, transferring the pattern to the organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask, and further etching the work using the pattern-transferred organic film as a mask to form a pattern.
Since the silicon-containing resist intermediate film of the 3-layer resist process exhibits etching resistance by oxygen gas or hydrogen gas, dry etching of the organic film using the silicon-containing resist intermediate film as a mask is preferably performed using an etching gas mainly containing oxygen gas or hydrogen gas in the 3-layer resist process.
As the silicon-containing resist intermediate film for the 3-layer resist treatment, a polysiloxane-based intermediate film is preferably used. By providing the silicon-containing resist intermediate film with an antireflection effect, reflection can be suppressed. In particular, for 193nm exposure, when a material containing a large amount of aromatic groups and having high etching selectivity to the substrate is used as the organic film, the k value becomes high and the substrate reflection becomes high, but the substrate reflection can be reduced to 0.5% or less by providing the material as an intermediate film of a silicon-containing resist with absorption having an appropriate k value to suppress reflection. For the silicon-containing resist intermediate film having an antireflective effect, it is preferable to use a light-absorbing group having a pendant anthracene group for exposure at 248nm and 157nm, and to use a polysiloxane crosslinked by acid or heat having a light-absorbing group having a pendant phenyl group or silicon-silicon bond for exposure at 193 nm.
In addition, a 4-layer resist process using an organic anti-reflection film is also suitable, and in this case, a circuit pattern of a semiconductor device can be formed on a substrate by a pattern forming method having at least the following steps:
forming an organic film on a workpiece using the above composition for forming an organic film, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming an organic anti-reflective coating (BARC) on the silicon-containing resist intermediate film, forming a resist upper film on the BARC using a photoresist composition to form a 4-layer film structure, forming a circuit pattern on the resist upper film, transferring the pattern to the BARC film and the silicon-containing resist intermediate film by etching using the patterned resist upper film as a mask, transferring the pattern to the organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask, and further etching the workpiece using the pattern-transferred organic film as a mask to form a pattern on the workpiece.
In addition, an inorganic hard mask may be formed instead of the silicon-containing resist intermediate film, and in this case, a circuit pattern of a semiconductor device can be formed on a substrate by a pattern forming method having at least the following steps: forming an organic film on a workpiece using the composition for forming an organic film, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition, forming a circuit pattern on the resist upper layer film, etching the inorganic hard mask using the patterned resist upper layer film as a mask, etching the organic film using the patterned inorganic hard mask as a mask, and further etching the workpiece using the patterned organic film as a mask to form a pattern on the workpiece.
As described above, when the inorganic hard mask is formed on the organic film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, a method for forming a silicon nitride film is described in Japanese patent application laid-open No. 2002-334869 and International publication No. 2004/066377. The thickness of the inorganic hard mask is preferably 5 to 200nm, more preferably 10 to 100nm. Further, as the inorganic hard mask, an SiON film having a high effect as an antireflection film is most preferably used. The substrate temperature for forming the SiON film is 300 to 500 ℃, and thus the SiON film needs to be able to withstand a temperature of 300 to 500 ℃ as an organic film. The organic film-forming composition used in the present invention has high heat resistance and can withstand a high temperature of 300 to 500 ℃, and therefore, an inorganic hard mask formed by a CVD method or an ALD method can be combined with an organic film formed by a spin coating method.
In addition, the method is also suitable for 4-layer resist processing using an organic anti-reflection film, and in this case, a circuit pattern of a semiconductor device can be formed on a substrate by at least a pattern forming method having the steps of: forming an organic film on a workpiece using the composition for forming an organic film, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a BARC on the inorganic hard mask, forming a resist upper layer film on the BARC using a photoresist composition to form a 4-layer film structure, forming a circuit pattern on the resist upper layer film, etching the patterned resist upper layer film using the BARC film and the inorganic hard mask as a mask, etching the organic film using the patterned inorganic hard mask as a mask, and further etching the workpiece using the patterned organic film as a mask to form a pattern on the workpiece.
As described above, a photoresist film may be formed on the inorganic hard mask as a resist upper layer film, or an organic anti-reflective coating (BARC) may be formed on the inorganic hard mask by spin coating and a photoresist film may be formed thereon. In particular, in the case of using the SiON film as the inorganic hard mask, the 2-layer antireflection film of the SiON film and the BARC can suppress reflection even in the immersion exposure with a high NA exceeding 1.0. Another advantage of forming the BARC is the effect of reducing the smear of the photoresist pattern directly over the SiON film.
The resist upper layer film in the 3-layer resist treatment may be a positive type or a negative type, and the same photoresist composition as a commonly used photoresist composition may be used. After spin-coating the photoresist composition, prebaking is carried out preferably at 60 to 180 ℃ for 10 to 300 seconds. Then, exposure was performed by a usual method, and further, post-exposure baking (PEB) and development were performed to obtain a resist pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 30 to 500nm, particularly preferably 50 to 400nm.
The exposure light is a high-energy radiation having a wavelength of 300nm or less, and specifically includes excimer laser beams having a wavelength of 248nm, 193nm or 157nm, soft X-rays having a wavelength of 3 to 20nm, electron beams, X-rays, and the like.
As a method for forming a pattern of the resist upper layer film, photolithography with a wavelength of 10nm to 300nm, direct drawing by an electron beam, nanoimprint, or a combination thereof is preferable.
In addition, the development method in the above-mentioned pattern forming method is preferably alkali development or development with an organic solvent.
Then, etching is performed using the obtained resist pattern as a mask. Etching of the silicon-containing resist intermediate film and the inorganic hard mask in the 3-layer resist treatment was performed using a fluorocarbon-based gas with the upper resist pattern as a mask. Thereby, a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern are formed.
Then, the obtained silicon-containing resist intermediate film pattern and inorganic hard mask pattern are used as masks, and etching processing of the organic film is performed.
The subsequent etching of the substrate to be processed can also be carried out by conventional methods, for example if the substrate to be processed is SiO 2 SiN or silica-based low dielectric constant insulating films are etched mainly with chlorofluorocarbon-based gases, and p-Si, al, and W are etched mainly with chlorine-based or bromine-based gases. When a substrate is processed and etched with a chlorofluorocarbon gas, the silicon-containing resist intermediate film pattern in the 3-layer resist process is peeled off at the same time as the substrate is processed. When a substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist intermediate film pattern needs to be peeled off by dry etching using a chlorofluorocarbon-based gas after the substrate is processed.
The organic film obtained from the composition for forming an organic film of the present invention is characterized by excellent etching resistance when etching the substrate to be processed.
The object to be processed (substrate to be processed) is not particularly limited, and Si, α -Si, p-Si, siO and the like can be used 2 And substrates such as SiN, siON, W, tiN, and Al, and processed layers formed on the substrates. Si and SiO are used as the layer to be processed 2 Various Low-k films such as SiON, siN, p-Si, α -Si, W-Si, al, cu, al-Si, etc., and barrier films thereof can be formed to a thickness of usually 50 to 10,000nm, particularly 100 to 5,000nm. In the case of forming a layer to be processed, a material different from that of the substrate and the layer to be processed may be used.
The object to be processed is preferably a semiconductor device substrate, or a semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed, and more specifically, si, α -Si, p-Si, siO, or the like can be used without particular limitation 2 And a substrate made of SiN, siON, W, tiN, al, or the like, and a layer to be processed, such as the metal film, is formed on the substrate.
As the layer to be processed, si or SiO can be used 2 Various Low-k films such as SiON, siN, p-Si, α -Si, W-Si, al, cu, al-Si, etc., and barrier films thereof can be formed to a thickness of usually 50 to 10,000nm, particularly 100 to 5,000nm. In the case of forming a layer to be processed, a material different from that of the substrate and the layer to be processed may be used.
Further, the metal constituting the object to be processed is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, ruthenium, or an alloy thereof.
Further, as the object to be processed, it is preferable to use a structure having a height of 30nm or more or a processed object having a step difference.
An example of the 3-layer resist process is specifically shown in fig. 1 and described below. In the case of 3-layer resist processing, as shown in fig. 1 (a), after an organic film 3 is formed on a layer 2 to be processed laminated on a substrate 1 using the composition for forming an organic film of the present invention, a silicon-containing resist intermediate film 4 is formed, and a resist upper film 5 is formed thereon.
Then, as shown in fig. 1B, the resist upper layer film 5 is exposed to light, PEB, and developed at the portion 6 to be used, thereby forming a resist pattern 5a (fig. 1C). Using the obtained resist pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using a CF gas, thereby forming a silicon-containing resist intermediate film pattern 4a ((D) of fig. 1). After the resist pattern 5a is removed, the organic film 3 is subjected to oxygen plasma etching using the obtained silicon-containing resist intermediate film pattern 4a as a mask, thereby forming an organic film pattern 3a ((E) of fig. 1). Further, after the silicon-containing resist intermediate film pattern 4a is removed, the layer to be processed 2 is etched using the organic film pattern 3a as a mask, thereby forming a pattern 2a ((F) of fig. 1).
In the case of using an inorganic hard mask, the silicon-containing resist intermediate film 4 is an inorganic hard mask, and a BARC layer is provided between the silicon-containing resist intermediate film 4 and the resist upper film 5 when BARC is applied. The etching of the BARC may be continuously performed before the etching of the silicon-containing resist intermediate film 4, or the etching of the silicon-containing resist intermediate film 4 may be performed by changing an etching apparatus or the like only after the etching of the BARC.
As described above, according to the pattern forming method of the present invention, a fine pattern can be formed on a substrate to be processed with high accuracy in a multilayer resist process.
In particular, since the present invention uses the organic film-forming composition containing the organic solvent, and the compound represented by the above general formula (1) and/or the polymer having the repeating unit represented by the above general formula (3) as the organic film-forming material, a fine pattern can be formed on a work with higher accuracy in the multilayer resist process.
[ examples ]
The present invention will be described more specifically below with reference to synthetic examples, and comparative examples, but the present invention is not limited to these examples. Further, as the molecular weight and the dispersity, a weight average molecular weight (Mw) and a number average molecular weight (Mn) in terms of polystyrene obtained by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a separation solution were obtained, and the dispersity (Mw/Mn) was obtained.
[ Synthesis example ] Synthesis of Compound and Polymer for organic film Forming Material
In the synthesis of the compounds (A1) to (a 16), the polymers (a 17) to (a 19) and the polymers (R1) to (R3) for comparative examples, the compounds (B1) to (B7) were used as phenols or naphthols, the compounds (C1) to (C3) were used as bis (indole-2, 3-diones), and the compounds (D1) and (D2) were used as aldehydes, as shown below. Furthermore, (D-1) used was a 37% aqueous solution.
Phenol or naphthols:
[ solution 33]
Figure BDA0003865932440000551
Bis (indole-2, 3-diones):
[ chemical 34]
Figure BDA0003865932440000561
Aldehydes:
[ solution 35]
Figure BDA0003865932440000562
The bis (indole-2, 3-dione) compounds represented above were synthesized in the following manner.
(Synthesis example 1)
Synthesis of Compound (C1)
[ solution 36]
Figure BDA0003865932440000563
Under a nitrogen atmosphere, 73.6g of indole-2, 3-dione, 207.3g of potassium carbonate and 900g of DMF (dimethylformamide) were added to prepare a uniform dispersion at an inner temperature of 50 ℃. 205.1g of 1, 4-dibromobutane was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 24 hours. After completion of the reaction, the reaction mixture was added to 5000ml of pure water to precipitate crystals. The precipitated crystals were separated by filtration, washed 3 times with 1000ml of pure water, then 2 times with 1000ml of methanol and recovered. The recovered crystals were vacuum-dried at 70 ℃ to obtain compound (C1).
(Synthesis example 2)
Synthesis of Compound (C2)
[ solution 37]
Figure BDA0003865932440000571
Under a nitrogen atmosphere, 73.6g of indole-2, 3-dione, 207.3g of potassium carbonate and 900g of DMF were added thereto, and the mixture was dispersed at an internal temperature of 50 ℃ to prepare a uniform dispersion. 231.8g of 1, 6-dibromohexane was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 24 hours. After completion of the reaction, the reaction mixture was added to 5000ml of pure water to precipitate crystals. The precipitated crystals were separated by filtration, washed 3 times with 1000ml of pure water, then 2 times with 1000ml of methanol and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (C2).
(Synthesis example 3)
Synthesis of Compound (C3)
[ solution 38]
Figure BDA0003865932440000572
Under a nitrogen atmosphere, 107.6g of 7- (trifluoromethyl) indole-2, 3-dione, 207.3g of potassium carbonate and 900g of DMF were added to prepare a uniform dispersion at an inner temperature of 50 ℃. 205.1g of 1, 4-dibromobutane was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 24 hours. After completion of the reaction, the reaction mixture was added to 6000ml of pure water to precipitate crystals. The precipitated crystals were separated by filtration, washed 3 times with 1000ml of pure water, then 2 times with 1000ml of methanol and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (C3).
The synthesis of the compounds (A1) to (a 16), the polymers (a 17) to (a 19), and the polymers (R1) to (R3) for the comparative examples was performed in the following manner.
(Synthesis example 4)
Synthesis of Compound (A1)
[ solution 39]
Figure BDA0003865932440000581
Under a nitrogen atmosphere, 11.9g of the compound (B1), 10.0g of the compound (C1), 8.3g of methanesulfonic acid and 100g of methylene chloride were added to prepare a uniform dispersion at room temperature, and then 0.3g of 3-mercaptopropionic acid was added to conduct a reaction at room temperature for 8 hours. After completion of the reaction, 200ml of MIBK (methyl isobutyl ketone) was added at room temperature, and the mixture was washed 6 times with 100ml of pure water, and the organic layer was dried under reduced pressure. 60g of MIBK was added to the residue to prepare a homogeneous solution, and then 300g of IPE (diisopropyl ether) was added to precipitate crystals. The precipitated crystals were separated by filtration, washed 2 times with 100g of IPE and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A1).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A1)：Mw＝740、Mw/Mn＝1.02
(Synthesis example 5)
Synthesis of Compound (A2)
[ solution 40]
Figure BDA0003865932440000591
13.9g of the compound (B2), 10.0g of the compound (C1), 8.3g of methanesulfonic acid and 100g of methylene chloride were added under a nitrogen atmosphere to prepare a uniform dispersion at room temperature, and then 0.3g of 3-mercaptopropionic acid was added to the mixture to carry out a reaction at room temperature for 8 hours. After the completion of the reaction, the reaction mixture was cooled in an ice bath to precipitate crystals. After 300g of IPE was added and stirred to disperse, the precipitated crystals were separated by filtration, and recovered by washing 100g of IPE 5 times. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A2).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A2)：Mw＝820、Mw/Mn＝1.01
(Synthesis example 6)
Synthesis of Compound (A3)
[ solution 41]
Figure BDA0003865932440000592
Under a nitrogen atmosphere, 18.2g of the compound (B3), 10.0g of the compound (C1) and 120g of methylene chloride were added to prepare a uniform dispersion at room temperature, and then 12.9g of trifluoromethanesulfonic acid was slowly added dropwise thereto, followed by reaction at room temperature for 8 hours. After completion of the reaction, 200ml of MIBK was added, and the mixture was washed 6 times with 100ml of pure water, and the organic layer was dried under reduced pressure. After 60g of MIBK was added to the residue to prepare a homogeneous solution, 300g of IPE was used to precipitate crystals. The precipitated crystals were separated by filtration, washed 2 times with 100g of IPE and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A3).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A3)：Mw＝910、Mw/Mn＝1.03
(Synthesis example 7)
Synthesis of Compound (A4)
[ solution 42]
Figure BDA0003865932440000601
20.2g of the compound (B4), 10.0g of the compound (C1) and 120g of methylene chloride were added under a nitrogen atmosphere to prepare a uniform dispersion at room temperature, and then 12.9g of trifluoromethanesulfonic acid was slowly added dropwise thereto to carry out a reaction at room temperature for 8 hours. After completion of the reaction, 200ml of MIBK was added, and the mixture was washed 6 times with 100ml of pure water, and the organic layer was dried under reduced pressure. 80g of MIBK was added to the residue to prepare a homogeneous solution, and then, crystals were precipitated from 300g of IPE. The precipitated crystals were separated by filtration, washed 2 times with 100g of IPE and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A4).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A4)：Mw＝960、Mw/Mn＝1.05
(Synthesis example 8)
Synthesis of Compound (A5)
[ solution 43]
Figure BDA0003865932440000611
Under a nitrogen atmosphere, 11.0g of the compound (B1), 10.0g of the compound (C2), 7.7g of methanesulfonic acid and 100g of methylene chloride were added to prepare a uniform dispersion at room temperature, and then 0.3g of 3-mercaptopropionic acid was added to conduct a reaction at room temperature for 8 hours. After completion of the reaction, 200ml of MIBK was added, and the mixture was washed 6 times with 100ml of pure water, and the organic layer was dried under reduced pressure. 60g of MIBK was added to the residue to prepare a homogeneous solution, and then, crystals were precipitated from 300g of IPE. The precipitated crystals were separated by filtration, washed 2 times with 100g of IPE and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A5).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A5)：Mw＝760、Mw/Mn＝1.02
(Synthesis example 9)
Synthesis of Compound (A6)
[ solution 44]
Figure BDA0003865932440000612
12.9g of the compound (B2), 10.0g of the compound (C2), 7.7g of methanesulfonic acid and 100g of methylene chloride were added under a nitrogen atmosphere to prepare a uniform dispersion at room temperature, and then 0.3g of 3-mercaptopropionic acid was added to the mixture to carry out a reaction at room temperature for 8 hours. After the reaction, the reaction mixture was cooled in an ice bath to precipitate crystals. After 300g of IPE was added and stirred to disperse, the precipitated crystals were separated by filtration, washed 5 times with 100g of IPE, and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A6).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A6)：Mw＝820、Mw/Mn＝1.01
(Synthesis example 10)
Synthesis of Compound (A7)
[ solution 45]
Figure BDA0003865932440000621
10.0g of compound (B2), 10.0g of compound (C3), 6.0g of methanesulfonic acid and 100g of dichloromethane were added under a nitrogen atmosphere to prepare a uniform dispersion at room temperature, and then 0.2g of 3-mercaptopropionic acid was added to conduct a reaction at room temperature for 8 hours. After completion of the reaction, 100ml of MIBK and 100ml of THF were added, and the mixture was washed 6 times with 100ml of pure water, and the organic layer was dried under reduced pressure. After 60g of THF was added to the residue to prepare a homogeneous solution, crystals were precipitated from the solution in 300g of hexane. The precipitated crystals were separated by filtration, washed 2 times with 100g of hexane and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A7).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A7)：Mw＝890、Mw/Mn＝1.01
(Synthesis example 11)
Synthesis of Compound (A8)
[ chemical formula 46]
Figure BDA0003865932440000631
13.1g of the compound (B3), 10.0g of the compound (C3) and 100g of methylene chloride were added under a nitrogen atmosphere to prepare a uniform dispersion at room temperature, and then 9.3g of trifluoromethanesulfonic acid was slowly added dropwise thereto to carry out a reaction at room temperature for 8 hours. After completion of the reaction, 200ml of MIBK was added, and the mixture was washed 6 times with 100ml of pure water, and the organic layer was dried under reduced pressure. After 60g of THF was added to the residue to prepare a homogeneous solution, crystals were precipitated in 300g of IPE. The precipitated crystals were separated by filtration, washed 2 times with 100g of IPE and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A8).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A8)：Mw＝1030、Mw/Mn＝1.04
(Synthesis example 12)
Synthesis of Compound (A9)
[ solution 47]
Figure BDA0003865932440000632
Under a nitrogen atmosphere, 10.0g of compound (A1), 12.0g of potassium carbonate and 60g of DMF were added to prepare a uniform dispersion at an internal temperature of 50 ℃. 8.6g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50 ℃ for 16 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. To the residue was added 40g of MIBK to prepare a homogeneous solution, and then 200g of MeOH (methanol) was added to precipitate crystals. The precipitated crystals were isolated by filtration, washed 2 times with 100g of MeOH and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A9).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A9)：Mw＝880、Mw/Mn＝1.02
(Synthesis example 13)
Synthesis of Compound (A10)
[ solution 48]
Figure BDA0003865932440000641
Under a nitrogen atmosphere, 10.0g of compound (A2), 22.0g of potassium carbonate and 80g of DMF were added to the mixture to prepare a uniform dispersion at an internal temperature of 50 ℃. 15.8g of propargyl bromide was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 24 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. 40g of MIBK was added to the residue to prepare a homogeneous solution, which was then crystallized from 200g of MeOH (methanol). The crystals that settled were isolated by filtration, washed 2 times with 100g of MeOH and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A10).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A10)：Mw＝1060、Mw/Mn＝1.03
(Synthesis example 14)
Synthesis of Compound (A11)
[ solution 49]
Figure BDA0003865932440000651
Under a nitrogen atmosphere, 10.0g of compound (A3), 9.3g of potassium carbonate and 40g of DMF were added to prepare a uniform dispersion at an internal temperature of 50 ℃. 6.7g of propargyl bromide was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 16 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. 40g of MIBK was added to the residue to prepare a homogeneous solution, which was then crystallized from 200g of MeOH (methanol). The precipitated crystals were isolated by filtration, washed 2 times with 100g of MeOH and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A11).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A11)：Mw＝1080、Mw/Mn＝1.05
(Synthesis example 15)
Synthesis of Compound (A12)
[ solution 50]
Figure BDA0003865932440000652
Under a nitrogen atmosphere, 10.0g of compound (A4), 9.0g of potassium carbonate and 40g of DMF were added to the mixture to prepare a uniform dispersion at an internal temperature of 50 ℃. 6.5g of propargyl bromide was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 16 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. 40g of MIBK was added to the residue to prepare a homogeneous solution, which was then crystallized from 200g of MeOH (methanol). The precipitated crystals were isolated by filtration and washed 2 times with 100g of MeOH for recovery. The recovered crystals were vacuum-dried at 70 ℃ to obtain compound (a 12).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A12)：Mw＝1110、Mw/Mn＝1.05
(Synthesis example 16)
Synthesis of Compound (A13)
[ solution 51]
Figure BDA0003865932440000661
Under a nitrogen atmosphere, 10.0g of compound (A5), 11.6g of potassium carbonate and 60g of DMF were added to the mixture to prepare a uniform dispersion at an internal temperature of 50 ℃. 8.6g of allyl bromide was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 16 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. After 40g of MIBK was added to the residue to prepare a homogeneous solution, the solution was crystallized from 200g of MeOH (methanol). The precipitated crystals were isolated by filtration, washed 2 times with 100g of MeOH and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A13).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A13)：Mw＝900、Mw/Mn＝1.02
(Synthesis example 17)
Synthesis of Compound (A14)
[ solution 52]
Figure BDA0003865932440000671
Under a nitrogen atmosphere, 10.0g of compound (A6), 21.4g of potassium carbonate and 80g of DMF were added to prepare a uniform dispersion at an internal temperature of 50 ℃. 15.2g of propargyl bromide was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 24 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. 40g of MIBK was added to the residue to prepare a homogeneous solution, which was then crystallized from 200g of MeOH (methanol). The precipitated crystals were isolated by filtration, washed 2 times with 100g of MeOH and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (a 14).
The weight average molecular weight (Mw) and the dispersity (Mw/Mn) were determined by GPC and were as follows.
(A14)：Mw＝1130、Mw/Mn＝1.03
(Synthesis example 18)
Synthesis of Compound (A15)
[ chemical formula 53]
Figure BDA0003865932440000681
Under a nitrogen atmosphere, 10.0g of compound (A7), 18.7g of potassium carbonate and 80g of DMF were added to the mixture to prepare a uniform dispersion at an internal temperature of 50 ℃. 13.3g of propargyl bromide was added slowly, and the reaction was carried out at an internal temperature of 50 ℃ for 24 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. 40g of MIBK was added to the residue to prepare a homogeneous solution, which was then crystallized from 200g of MeOH (methanol). The precipitated crystals were isolated by filtration, washed 2 times with 100g of MeOH and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A15).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A15)：Mw＝1130、Mw/Mn＝1.03
(Synthesis example 19)
Synthesis of Compound (A16)
[ formula 54]
Figure BDA0003865932440000682
Under a nitrogen atmosphere, 10.0g of compound (A8), 8.1g of potassium carbonate and 60g of DMF were added to the mixture to prepare a uniform dispersion at an internal temperature of 50 ℃. 5.9g of allyl bromide was added slowly, and the reaction was carried out at an internal temperature of 50 ℃ for 16 hours. After completion of the reaction, 100ml of MIBK was added, and the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. 40g of MIBK was added to the residue to prepare a homogeneous solution, which was then crystallized from 200g of MeOH (methanol). The precipitated crystals were isolated by filtration, washed 2 times with 100g of MeOH and recovered. The recovered crystals were dried under vacuum at 70 ℃ to obtain compound (A16).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A16)：Mw＝1220、Mw/Mn＝1.05
(Synthesis example 20)
Synthesis of Polymer (A17)
[ solution 55]
Figure BDA0003865932440000691
Under a nitrogen atmosphere, 5.0g of the compound (A9), 0.19g of the compound (D1) and 50g of 1, 2-dichloroethane were added to prepare a uniform solution at an internal temperature of 50 ℃. 0.5g of methanesulfonic acid was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, 100ml of MIBK was added, the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. After 20g of THF was added to the residue to prepare a homogeneous solution, crystals were precipitated in 100g of hexane. The precipitated crystals were separated by filtration, washed 2 times with 50g of hexane and recovered. The recovered crystals were vacuum-dried at 70 ℃ to obtain a polymer (A17).
The weight average molecular weight (Mw) and the dispersity (Mw/Mn) were determined by GPC and were as follows.
(A17)：Mw＝2700、Mw/Mn＝1.58
(Synthesis example 21)
Synthesis of Polymer (A18)
[ chemical 56]
Figure BDA0003865932440000701
Under a nitrogen atmosphere, 5.0g of the compound (A11), 0.12g of the compound (D1) and 50g of 1, 2-dichloroethane were added to prepare a uniform solution at an internal temperature of 50 ℃. 0.5g of methanesulfonic acid was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, 100ml of MIBK was added, the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. After 20g of THF was added to the residue to prepare a homogeneous solution, crystals were precipitated in 100g of hexane. The precipitated crystals were separated by filtration, washed 2 times with 50g of hexane and recovered. The recovered crystals were vacuum-dried at 70 ℃ to obtain a polymer (A18).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(A18)：Mw＝3300、Mw/Mn＝1.45
(Synthesis example 22)
Synthesis of Polymer (A19)
[ solution 57]
Figure BDA0003865932440000711
Under a nitrogen atmosphere, 5.0g of the compound (A14), 0.29g of the compound (D2) and 50g of 1, 2-dichloroethane were added to prepare a uniform solution at an internal temperature of 50 ℃. 0.5g of methanesulfonic acid was slowly added thereto, and the reaction was carried out at an internal temperature of 50 ℃ for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, 100ml of MIBK was added, the mixture was washed 6 times with 50ml of pure water, and the organic layer was dried under reduced pressure. After 20g of THF was added to the residue to prepare a homogeneous solution, crystals were precipitated from the solution in 100g of hexane. The precipitated crystals were separated by filtration, washed 2 times with 50g of hexane and recovered. The recovered crystals were vacuum-dried at 70 ℃ to obtain polymer (A19).
The weight average molecular weight (Mw) and the dispersity (Mw/Mn) were determined by GPC and were as follows.
(A19)：Mw＝3600、Mw/Mn＝1.59
(Synthesis example 23)
Synthesis of Polymer (R1) for comparative example
[ solution 58]
Figure BDA0003865932440000712
31.8g of compound (B5), 4.9g of compound (D1), 5.0g of oxalic acid, and 50g of dioxane were added under a nitrogen atmosphere, and a reaction was carried out at an internal temperature of 100 ℃ for 24 hours. After completion of the reaction, 500ml of MIBK was added at room temperature, and washed 6 times with 100ml of pure water. The organic layer was collected, and the water and solvent were removed under reduced pressure to 2mmHg at an internal temperature of 150 ℃ to obtain a polymer (R1) for a comparative example.
The weight average molecular weight (Mw) and the dispersity (Mw/Mn) were determined by GPC and were as follows.
(R1)：Mw＝3200、Mw/Mn＝4.88
(Synthesis example 24)
Synthesis of Polymer (R2) for comparative example
[ chemical 59]
Figure BDA0003865932440000721
42.3g of the compound (B6), 5.7g of the compound (D1), 5.0g of oxalic acid and 60g of dioxane were added under a nitrogen atmosphere, and a reaction was carried out at an internal temperature of 100 ℃ for 24 hours. After completion of the reaction, 500ml of MIBK was added at room temperature, and washed 6 times with 100ml of pure water. The organic layer was collected, and the water and solvent were removed under reduced pressure to 2mmHg at an internal temperature of 150 ℃ to obtain a polymer (R2) for a comparative example.
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(R2)：Mw＝2600、Mw/Mn＝3.55
(Synthesis example 25)
Synthesis of Polymer (R3) for comparative example
[ solution 60]
Figure BDA0003865932440000731
Under a nitrogen atmosphere, 3.1g of indole-2, 3-dione, 10.0g of the compound (B7), 3.0g of methylsulfone, 16.1g of propylene glycol monomethyl ether, and 3.4g of 3-mercaptopropionic acid were added, and the mixture was heated to 140 ℃ and reacted under reflux for 4 hours. After the reaction was completed, 200g of methanol/pure water =1/1 (weight ratio) was added dropwise to precipitate crystals. The precipitated crystals were separated by filtration, washed 2 times with 100g of pure water and recovered. The recovered crystals were vacuum-dried at 60 ℃ to obtain a polymer (R3) for comparative example.
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were determined by GPC, and the results were as follows.
(R3)：Mw＝8500、Mw/Mn＝2.30
The results of Mw and Mw/Mn of the compounds (A1) to (A16), the polymers (A17) to (A19) and the polymers (R1) to (R3) for comparative examples used in examples are shown in tables 1 to 4.
[ Table 1]
Figure BDA0003865932440000741
/>
Figure BDA0003865932440000751
[ Table 2]
Figure BDA0003865932440000752
/>
Figure BDA0003865932440000761
[ Table 3]
Figure BDA0003865932440000771
/>
Figure BDA0003865932440000781
[ Table 4]
Figure BDA0003865932440000782
[ preparation of compositions for organic film formation (UDL-1 to 26, comparative UDL-1 to 9) ]
The compounds and polymers (A1) to (a 19) described above, the polymers (R1) to (R3) for comparative examples, the compounds (B5) and (B6) described in the above synthesis examples, the crosslinking agent (XL), the Thermal Acid Generator (TAG), and (S1) 1, 6-diacetoxyhexane as a high boiling point solvent: boiling point 260 ℃, (S2) tripropylene glycol monomethyl ether: propylene Glycol Monomethyl Ether Acetate (PGMEA) having a boiling point of 242 ℃ and containing 0.1 mass% of PF-6320 (manufactured by OMNOVA) was dissolved at the ratio shown in Table 5, and the solution was filtered through a 0.1 μm fluororesin filter to prepare organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9), respectively.
The structural formulae of the compound, the crosslinking agent, and the thermal acid generator used in the composition for forming an organic film are shown below.
(Compound (I))
[ solution 61]
Figure BDA0003865932440000791
(crosslinking agent)
[ chemical formula 62]
Figure BDA0003865932440000792
(thermal acid Generator)
[ solution 63]
Figure BDA0003865932440000801
[ Table 5]
Figure BDA0003865932440000802
Figure BDA0003865932440000811
< evaluation >
[ measurement of solvent resistance (examples 1-1 to 1-26 and comparative examples 1-1 to 1-9) ]
The UDL-1 to 26 and comparative UDL-1 to 9 prepared above were applied to a silicon substrate, baked at a temperature shown in table 6 in the atmosphere for 60 seconds, and then the film thickness was measured, a PGMEA solvent was dispensed thereon, and the substrate was left to stand for 30 seconds to be spin-dried, baked at 100 ℃ for 60 seconds to evaporate PGMEA, and the film thickness before and after PGMEA treatment was measured. The residual film ratio was determined using the film thickness after film formation and the film thickness after PGMEA treatment. The results are shown in Table 6.
[ Table 6]
Figure BDA0003865932440000812
Figure BDA0003865932440000821
As shown in table 6, it was found that the organic films (examples 1-1 to 1-26) using the compound and/or the polymer of the present invention exhibited sufficient solvent resistance because the residual film ratio after PGMEA treatment was 99.5% or more and a crosslinking reaction was caused by heat treatment. In comparative examples 1-1 to 1-16 and comparative examples 1-1 to 1-4 and 1-7 to 1-9, the compound of the present invention exerts sufficient curing properties regardless of a single molecule, but in comparative examples 1-7 and 1-8, in which only a single-molecule compound is used, the curing properties are insufficient, the heat resistance is insufficient, or the molecular weight is small, so that solvent resistance cannot be obtained due to sublimation or the like, and a crosslinking agent needs to be added to ensure solvent resistance as in comparative examples 1-9. In comparative examples 1-2 and 1-4 in which polymers were mixed, as in comparative examples 1-1 and 1-3, the curability was ensured by the polymer alone, but as described above, it was considered that solvent resistance could not be ensured due to insufficient curability, heat resistance, sublimation, and the like. In comparative examples 1 to 5 and 1 to 6, the polymer alone does not exhibit curability regardless of the use of the polymer, and it is necessary to add a crosslinking agent or a thermal acid generator to ensure solvent resistance.
[ evaluation of Heat resistance Properties (examples 2-1 to 2-26 and comparative examples 2-1 to 2-9) ]
The organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9) were each coated on a silicon substrate, and then baked in the air at a temperature shown in Table 7 for 60 seconds to form a coating film having a thickness of about 200nm, and the film thickness A was measured. The substrate was further calcined at 400 ℃ for 20 minutes under a nitrogen gas flow of 0.2 vol% or less under an oxygen concentration control, and the film thickness B was measured. These results are shown in Table 7.
[ Table 7]
Figure BDA0003865932440000831
As shown in Table 7, it was found that the compositions for forming an organic film of the present invention (examples 2-1 to 2-26) had a film thickness decreased by less than 2% after baking at 400 ℃ for a long period of time, and were excellent in heat resistance. In particular, the compound and the polymer having propargyloxy groups introduced as substituents maintain a residual film ratio of 99% or more, and are particularly excellent in heat resistance.
On the other hand, in comparative examples 2-1 to 2-9, the residual film ratio was low in the case where the solvent resistance could not be obtained as a result of the solvent resistance measurement. Comparative examples 2-7 and 2-8 using the monomolecular compound hardly had any residual organic film, and comparative examples 2-1, 2-3 and 2-6, which were capable of securing solvent resistance by adding a crosslinking agent or using a polymer, were lower in residual film rate than examples of the present invention, and it was found that organic films using the compound and the polymer of the present invention were excellent in heat resistance.
[ evaluation of film Forming Properties (examples 3-1 to 3-26 and comparative examples 3-1 to 3-9) ]
The organic film-forming compositions (UDL-1 to 26, comparative examples UDL-1 to 9) prepared as described above were applied to a Bare-Si substrate, a Hexamethyldisilazane (HMDS) -treated substrate, and a SiON-treated substrate shown in Table 8, respectively, and then baked at the temperatures shown in Table 8 in the air for 60 seconds to form organic films having a film thickness of 100nm, and the presence or absence of coating abnormality of the formed organic films was observed with an optical microscope (ECLIPSE L200, manufactured by Nikon). In addition, in this evaluation, the film thickness is made thin in order to evaluate the quality of the coatability, and strict evaluation conditions are set such that film formation abnormality is likely to occur.
[ Table 8]
Figure BDA0003865932440000851
As shown in Table 8, it was found that the organic film-forming compositions of the present invention (examples 3-1 to 3-26) had no substrate dependency and could ensure film-forming properties. On the other hand, in comparative examples 3 to 7 and 3 to 8, as in the solvent resistance measurement and the heat resistance characteristic evaluation, the film forming property could not be secured due to insufficient curing property and heat resistance of the monomolecular compound and generation of sublimate. In addition, as in comparative examples 3-1 to 3-4 and 3-9, even if the crosslinking agent, the polymer addition and the polymer alone were added, the film forming property could not be secured depending on the substrate. From the comparison of the results, it is understood that the compound and the polymer of the present invention contribute to improvement of film-forming properties by the cyclic amide structure functioning as an adhesion group. In view of the same tendency, it is also understood that comparative examples 3-5 and 3-6 using a polymer having a cyclic amide structure cannot ensure film-forming properties when the polymer having no curing property and poor heat resistance is used alone, but comparative examples 3-6 using a cured film formed by adding a crosslinking agent have improved film-forming properties.
[ evaluation of filling characteristics (examples 4-1 to 4-26 and comparative examples 4-1 to 4-9) ]
The organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9) prepared above were applied to SiO having a dense hole pattern (hole diameter 0.16 μm, hole depth 0.50 μm, distance between centers of two adjacent holes 0.32 μm) respectively 2 The organic film was formed on the wafer substrate by firing in the air at the temperature shown in table 9 for 60 seconds. The substrate used was a base substrate 7 (SiO) having a dense hole pattern as shown in FIG. 2 (G) (top view) and (H) (cross-sectional view) 2 Wafer substrate). The cross-sectional shape of each wafer substrate obtained was observed with a Scanning Electron Microscope (SEM), and it was confirmed whether or not the inside of the hole was filled with the organic film 8 without a gap. The results are shown in table 9, and in this evaluation, voids were generated in the pores when the composition for forming an organic film having poor filling properties was used. In the case where a composition for forming an organic film having good filling properties was used, the organic film was filled in the pores as shown in fig. 2 (I) in the present evaluation.
[ Table 9]
Figure BDA0003865932440000871
As shown in examples 4-1 to 4-26 of Table 9, when the compound and the polymer of the present invention were used, it was found that the hole pattern could be filled without any void regardless of the composition for forming an organic film, and the filling property was excellent. On the other hand, in comparative examples 4-1 to 4-5, 4-7 and 4-8, as the results of the solvent resistance measurement and the heat resistance evaluation, it is considered that the solvent resistance could not be secured and the heat resistance was insufficient, and thus the filling failure occurred. In addition, in comparative examples 4 to 6, it is considered that the use of the polymer while ensuring the solvent resistance results in poor thermal fluidity as compared with the monomolecular compound, and a rapid curing reaction occurs due to the action of the thermal acid generator, so that the thermal fluidity is insufficient and voids are generated due to the poor filling. On the other hand, comparative examples 4 to 9 are monomolecular compounds, and thus contribute to thermal fluidity, and thus can ensure landfill property.
[ evaluation of flattening Properties (examples 5-1 to 5-26 and comparative examples 5-1 to 5-9) ]
The organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9) prepared above were applied to a base substrate 9 (SiO) having a giant isolated trench pattern ((J) of FIG. 3, trench width 10 μm, trench depth 0.1 μm), respectively 2 Wafer substrate), and the substrate was baked in the air at the temperature described in table 10 for 60 seconds, and the difference in height between the organic film 10 in the trench portion and the organic film 10 in the non-trench portion was observed using an NX10 Atomic Force Microscope (AFM) manufactured by Park Systems corporation (delta 10 in fig. 3 (K). The results are shown in Table 10. In this evaluation, the smaller the difference in level, the better the planarization characteristics. In this evaluation, a trench pattern having a depth of 0.10 μm was planarized using an organic film-forming composition having a normal film thickness of about 0.2 μm, and strict evaluation conditions were used to evaluate the flatness characteristics.
[ Table 10]
Figure BDA0003865932440000891
As shown in examples 5-1 to 5-26 of Table 10, it is understood that in the case of using the compound and the polymer of the present invention, the difference in level between the organic film in the trench portion and the organic film in the non-trench portion is smaller and the planarization property is excellent in any of the organic film materials as compared with comparative examples 5-1 to 5-9. Particularly, the dehydration condensates of phenol or catechol with bis (indole-2, 3-diones) as in examples 5-9, 5-10, 5-14, 5-15, and having propargyl groups as substituents, exhibited good results. This is considered to be because the heat resistance is excellent from the heat resistance test results of the evaluation of the heat resistance characteristics, and because the viscosity of the compound in which the hydroxyl group is blocked by etherification is decreased. In comparative examples 5-1 to 5-5, 5-7 and 5-8, it is considered that as a result of the heat resistance test such as the evaluation of heat resistance characteristics, the film shrinkage during baking was large because of insufficient heat resistance, and therefore, a difference in level and a difference in film thickness occurred, and the planarization characteristics were deteriorated. In addition, in comparative examples 5 to 6 and 5 to 9, it is considered that since a crosslinking agent is used for securing solvent resistance, a rapid hardening reaction occurs, and the benefit of thermal fluidity is not obtained, and the planarization characteristics deteriorate. The polymers used in comparative examples 5 to 6 inherently lack thermal fluidity, and it can be inferred from the results apparent in comparative examples 5 to 9 that are monomolecular compounds. It is also understood that the flatness can be improved by adding a high boiling point solvent by comparing examples 5-23 to 5-26 with examples 5-1, 5-10, 5-11 and 5-18 without adding a solvent. Further, by comparing examples 5-20 to 5-22 in which the compound of the present invention and the polymer were mixed with examples 5-17 to 5-19 in which only the polymer was used, the planarization property was improved, and the planarization property could be improved by adjusting the amount of the compound without impairing various physical properties required for the organic film such as heat resistance, distortion resistance, and etching resistance.
[ adhesion test (examples 6-1 to 6-26 and comparative examples 6-1 to 6-4) ]
The organic film-forming compositions (UDL-1 to 26, comparative UDL1, 3, 6 and 9) were applied to SiO 2 The wafer substrate was baked at a temperature shown in Table 11 for 60 seconds in the atmosphere using a hot plate, thereby forming an organic film having a thickness of 200 nm. The wafer with the organic film was cut into a1 × 1cm square, and the wafer was cut out using a special jig and mounted with an aluminum pin with an epoxy adhesive. Thereafter, the aluminum pin was bonded to the substrate by heating at 150 ℃ for 1 hour using an oven. After cooling to room temperature, the initial adhesion was evaluated by the resistance force using a film adhesion strength measuring apparatus (Sebastian Five-A). Furthermore, comparative UDL-2, 4,5, 7, and 8, in which solvent resistance could not be ensured in the solvent resistance measurement, could not be subjected to the adhesion test.
FIG. 4 is an explanatory view showing a method of measuring adhesion. In fig. 4, reference numeral 11 denotes a silicon wafer (substrate), 12 denotes a cured coating, 13 denotes a support, 14 denotes an aluminum pin with an adhesive, 15 denotes a jig, and 16 denotes a stretching direction. The sealing force is an average value of 12-point measurement, and the higher the value, the higher the adhesion of the sealing film to the substrate. The adhesion was evaluated by comparing the obtained values. The results are shown in Table 11.
[ Table 11]
Figure BDA0003865932440000911
Figure BDA0003865932440000921
As shown in examples 6-1 to 6-26 of Table 11, it is understood that when the compound and the polymer of the present invention were used, the organic film material exhibited a higher adhesion force than comparative examples 6-1, 6-2, and 6-4. In addition, comparative example 6-3 exhibited high sealing force because it has a similar cyclic amide structure. From the results, it is considered that the effect of the heterocyclic structure introduced into the compound or polymer of the present invention improves the adhesion property, and as a result of the evaluation of the film-forming property, the film-forming property is excellent.
[ Pattern formation tests (examples 7-1 to 7-26 and comparative examples 7-1 to 7-4) ]
The organic film-forming compositions (UDL-1 to 26, comparative UDL1, 3, 6 and 9) were applied to SiO formed to a thickness of 200nm by HMDS treatment 2 An organic film was formed on a Bare Si substrate having a trench pattern (trench width 10 μm, trench depth 0.10 μm) by firing in the atmosphere under the conditions shown in Table 15 so that the film thickness on the Bare Si substrate became 200 nm. A silicon-containing resist intermediate film material (SOG-1) was applied thereon, baked at 220 ℃ for 60 seconds to form a resist intermediate film having a film thickness of 35nm, a photoresist composition (SL resist for ArF) was applied thereon, and baked at 105 ℃ for 60 seconds to form a resist upper film having a film thickness of 100nm. A wet protective film (TC-1) was applied to the resist upper layer film, and the resultant was baked at 90 ℃ for 60 seconds to form a protective film having a thickness of 50 nm. In addition, in the comparative examples UDL-2, 4,5, 7, and 8 in which solvent resistance could not be secured in the solvent resistance measurement, pattern formation tests could not be performed because a silicon-containing resist intermediate film could not be formed.
As a photoresist composition (SL resist for ArF), a polymer (RP 1), an acid generator (PAG 1), and a basic compound (Amine 1) were dissolved in a solvent containing FC-430 (manufactured by sumitomo 3M) in an amount of 0.1 mass% in the proportions shown in table 12, and filtered through a 0.1 μ M fluororesin filter.
[ Table 12]
Figure BDA0003865932440000931
The structural formulae of the polymer (RP 1), acid generator (PAG 1), and basic compound (Amine 1) used are shown below.
[ solution 64]
Figure BDA0003865932440000932
As the sizing film material (TC-1), a film polymer (PP 1) was dissolved in an organic solvent in the ratio shown in Table 13, and the solution was filtered through a 0.1 μm fluororesin filter.
[ Table 13]
Figure BDA0003865932440000941
The structural formula of the polymer (PP 1) used is shown below.
[ solution 65]
Figure BDA0003865932440000942
As a silicon-containing resist intermediate film material (SOG-1), a polymer represented by ArF silicon-containing intermediate film polymer (SiP 1) and a crosslinking catalyst (CAT 1) were dissolved in an organic solvent containing FC-4430 (manufactured by Sumitomo 3M) in an amount of 0.1 mass% in a ratio shown in Table 14, and the solution was filtered through a fluororesin filter having a pore size of 0.1. Mu.m, to prepare a silicon-containing resist intermediate film material (SOG-1).
[ Table 14]
Figure BDA0003865932440000943
The structural formulas of the ArF silicon-containing interlayer polymer (SiP 1) and the crosslinking catalyst (CAT 1) used are shown below.
[ solution 66]
Figure BDA0003865932440000951
Then, exposure was carried out by an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ 0.98/0.65, 35 degree dipole-S polarized illumination, 6% half-tone phase shift mask) while changing the exposure amount, baking (PEB) was carried out at 100 ℃ for 60 seconds, and development was carried out with 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a positive type line-and-space pattern with a pitch of 100nm and a resist line width of 50nm to 30 nm.
Then, a silicon-containing intermediate film was processed using a resist pattern as a mask, an organic film was processed using the silicon-containing intermediate film as a mask, and SiO was processed using the organic film as a mask by dry etching using Telius, a tokyo wiliki etching apparatus 2 And (5) processing the film.
The etching conditions are as follows.
(transfer conditions of resist Pattern to SOG film)
Figure BDA0003865932440000952
(transfer conditions for SOG film to organic film)
Figure BDA0003865932440000953
Figure BDA0003865932440000961
(for SiO) 2 Transfer conditions of film)
Figure BDA0003865932440000962
The cross section of the pattern was observed with an electron microscope (S-4700) made by Hitachi, ltd., and the shapes were compared, and the results are shown in Table 15.
[ Table 15]
Figure BDA0003865932440000963
Figure BDA0003865932440000971
As shown in Table 15, it was confirmed that the organic film forming composition of the present invention was suitable for use in microfabrication by the multilayer resist method, as was the result of the organic film forming composition of the present invention (examples 7-1 to 7-26), since the resist upper layer film pattern was successfully transferred to the substrate in the end in either case. On the other hand, in comparative examples 7-1, 7-2 and 7-3, as in the film forming evaluation, the pattern collapse occurred during the pattern processing due to the pin hole generated during the film forming, and the pattern could not be formed. In comparative examples 7 to 4, as a result of the film formation test for film formation evaluation, a pattern was not formed because of pattern collapse at the time of pattern processing due to pinholes generated at the time of film formation.
From the above facts, it is clear that the composition for forming an organic film of the present invention is excellent in film forming property and filling/planarizing property, and therefore, is extremely useful as an organic film material used in a multilayer resist method, and that the method for forming a pattern of the present invention using the composition for forming an organic film of the present invention can form a fine pattern with high accuracy even when a work is a substrate having a step.
The present invention is not limited to the above embodiment. The above embodiments are illustrative, and those having substantially the same configuration and exhibiting the same operational effects as the technical idea described in the claims of the present invention are included in the technical scope of the present invention.
Description of the reference numerals
1: substrate
2 layer to be processed
2a pattern formed on the layer to be processed
3 organic film
3a organic film pattern
4 silicon-containing resist intermediate film
4a silicon-containing resist intermediate film pattern
Resist top layer film
5a resist Pattern
6 used portion (Exposure portion)
Base substrate with dense hole pattern
8 organic film
9 base substrate with huge isolated trench pattern
10 organic film
delta 10 difference in film thickness of organic film between trench portion and non-trench portion
11 silicon wafer
12 hardening the coating
13 support table
14 aluminum pin with adhesive
15, a clamp
And 16, stretching direction.

Claims (25)

1. A composition for forming an organic film, comprising an organic film-forming material represented by the following general formula and an organic solvent;
Figure FDA0003865932430000011
in the general formula, R 1 Is a hydrogen atom, an allyl group, or a propargyl group, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a C1 to C4A 2-valent organic group of 0; each V independently represents a hydrogen atom or a linking moiety.
2. The composition for forming an organic film according to claim 1, wherein the organic film-forming material is a compound represented by the following general formula (1);
Figure FDA0003865932430000012
in the general formula (1), R 1 、R 2 M, n, l, k and W are the same as above.
3. The composition for forming an organic film according to claim 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2);
Figure FDA0003865932430000021
in the general formula (2), R 1 W and n are the same as above.
4. The composition for forming an organic film according to claim 2 or 3, wherein the compound has a ratio Mw/Mn of weight-average molecular weight Mw to number-average molecular weight Mn in terms of polystyrene calculated by gel permeation chromatography of 1.00. Ltoreq. Mw/Mn. Ltoreq.1.10.
5. The composition for forming an organic film according to claim 1, wherein the organic film-forming material is a polymer having a repeating unit represented by the following general formula (3);
Figure FDA0003865932430000022
r in the general formula (3) 1 、R 2 W, n, m, L and k are the same as above, and L is a C1-40 organic group having a valence of 2.
6. The composition for forming an organic film according to claim 5, wherein the polymer is a polymer having a repeating unit represented by the following general formula (4);
Figure FDA0003865932430000031
in the general formula (4), R 1 W, L and n are the same as above.
7. The composition for forming an organic film according to claim 5 or 6, wherein L is a 2-valent organic group represented by the following general formula (5);
Figure FDA0003865932430000032
in the general formula (5), R 3 Is a hydrogen atom or an organic group containing an aromatic ring having 1 to 20 carbon atoms, and the dotted line represents an atomic bond.
8. The composition for forming an organic film according to claim 5 or 6, wherein the weight average molecular weight of the polymer is 1000 to 5000.
9. The composition for forming an organic film according to claim 1, wherein the organic film-forming material contains 1 or more species each selected from a compound represented by the following general formula (1) and a polymer having a repeating unit represented by the following general formula (3);
Figure FDA0003865932430000033
in the general formula (1), R 1 、R 2 M, n, l, k and W are the same as above;
Figure FDA0003865932430000041
r in the general formula (3) 1 、R 2 W, n, m, L and k are the same as above, and L is a C1-40 organic group having a valence of 2.
10. The composition for forming an organic film according to any one of claims 1 to 3, wherein the organic solvent is a mixture of 1 or more organic solvents having a boiling point of less than 180 ℃ and 1 or more organic solvents having a boiling point of 180 ℃ or higher.
11. The composition for forming an organic film according to any one of claims 1 to 3, wherein the composition for forming an organic film further contains 1 or more of a surfactant and a plasticizer.
12. A pattern forming method comprising the steps of:
forming an organic film on a processed body using the composition for forming an organic film according to any one of claims 1 to 11,
forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material,
forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition,
forming a circuit pattern on the resist upper layer film,
the pattern is transferred to the silicon-containing resist intermediate film by etching using the patterned resist upper film as a mask,
transferring the pattern to an organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask,
further, the organic film of the transferred pattern is patterned by etching on the object to be processed using the organic film of the transferred pattern as a mask.
13. A pattern forming method comprising the steps of:
forming an organic film on a processed body using the composition for forming an organic film according to any one of claims 1 to 11,
forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material,
forming an organic anti-reflective coating (BARC) on the silicon-containing resist intermediate film,
a 4-layer film structure is formed on the BARC by using a photoresist composition,
forming a circuit pattern on the resist upper layer film,
transferring the pattern to the BARC film and the silicon-containing resist intermediate film by etching using the patterned resist upper film as a mask,
transferring the pattern to an organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask,
further, the processed body is etched by using the organic film with the transferred pattern as a mask to form a pattern on the processed body.
14. A pattern forming method comprising the steps of:
forming an organic film on a processed body using the composition for forming an organic film according to any one of claims 1 to 11,
forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film,
forming a resist upper layer film on the inorganic hard mask using a photoresist composition,
forming a circuit pattern on the resist upper layer film,
etching the inorganic hard mask using the patterned resist upper layer film as a mask,
the organic film is etched using the patterned inorganic hard mask as a mask,
further, the object to be processed is etched using the patterned organic film as a mask to form a pattern on the object to be processed.
15. A pattern forming method comprising the steps of:
forming an organic film on a processed body using the composition for forming an organic film according to any one of claims 1 to 11,
forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film,
a BARC is formed over the inorganic hard mask,
a 4-layer film structure is formed on the BARC by using a photoresist composition,
forming a circuit pattern on the resist upper layer film,
etching the BARC film and the inorganic hard mask using the patterned resist upper layer film as a mask,
the organic film is etched using the patterned inorganic hard mask as a mask,
further, the patterned organic film is used as a mask to etch the object to be processed, thereby forming a pattern on the object to be processed.
16. The pattern forming method according to claim 14 or 15, wherein the inorganic hard mask is formed by a CVD method or an ALD method.
17. The pattern forming method according to any one of claims 12 to 15, wherein the pattern formation of the resist upper layer film is performed by photolithography with a wavelength of 10nm to 300nm, direct drawing using an electron beam, nanoimprinting, or a combination thereof.
18. The pattern forming method according to any one of claims 12 to 15, wherein in the pattern forming method, exposure and development for forming a circuit pattern on the resist upper layer film are performed, and the development is alkali development or development using an organic solvent.
19. The pattern forming method according to any one of claims 12 to 15, wherein a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film is used as the object to be processed.
20. The pattern forming method according to claim 19, wherein the metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.
21. A compound represented by the following general formula (1):
Figure FDA0003865932430000071
in the general formula (1), R 1 Is a hydrogen atom, allyl, or propargyl, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms.
22. The compound according to claim 21, which is represented by the following general formula (2);
Figure FDA0003865932430000081
in the general formula (2), R 1 W and n are the same as above.
23. A polymer having a repeating unit represented by the following general formula (3):
Figure FDA0003865932430000082
in the general formula (3), R 1 Is a hydrogen atom, an allyl group, or a propargyl group, R 2 Represents nitro, halogen atom, hydroxyl, alkyloxy with 1-4 carbon atoms, alkynyl oxy with 2-4 carbon atoms, alkenyloxy with 2-4 carbon atoms, straight-chain, branched or cyclic alkyl with 1-6 carbon atoms, trifluoromethyl or trifluoromethyl oxy; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and the aromatic rings form a cyclic ether structure with each other when l = 1; k represents an integer of 0 to 2, and W is a 2-valent organic group having 1 to 40 carbon atoms; l is a C1-40 2-valent organic group.
24. The polymer according to claim 23, wherein the polymer has a repeating unit represented by the following general formula (4);
Figure FDA0003865932430000091
in the general formula (4), R 1 W, L, n are as described above.
25. The polymer according to claim 23 or 24, wherein L is a 2-valent organic group represented by the following general formula (5);
Figure FDA0003865932430000092
in the general formula (5), R 3 Is a hydrogen atom or an organic group containing an aromatic ring having 1 to 20 carbon atoms, and the dotted line represents an atomic bond.
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